TRIAMINOCYCLOPROPENIUM SALTS TECHNICAL FIELD

The present invention relates to salts comprising triaminocyclopropenium cations, to processes for the preparation of these salts, and to the use of these salts as ionic liquids.

BACKGROUND ART

Ionic liquids comprise ions and short-lived ion pairs, in contrast to conventional organic or aqueous solvents. They generally do not contain neutral molecules and usually have melting points below 373 K. These substances are also known as liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.

Ionic liquids have developed significantly over the past 10 years, particularly as they become available on industrial scales. The great attraction of these liquids stems from their properties of almost zero vapour pressure, low flammability and ease of recycling. For these reasons, they are frequently considered as potential green alternatives to classical organic solvents. Additionally, most classes of ionic liquid can be readily tuned to provide unique solvent environments in which to carry out reactions, extractions and other processes.

Currently, there are four major classes of ionic liquids (based on pyridinium, imidazolium, phosphonium and ammonium cations). Guanidinium salts have also been recently investigated.

The properties of ionic liquids, for example melting point, thermal and electrochemical stability and viscosity, are affected by the nature of both the cation and the anion. Similarly, the selection of cation and anion can affect the polarity and hydrophilicity/hydrophobicity of the resulting ionic liquid.

Triaminocyclopropenium salts were first identified in 1971 (Z. Yoshida and Y. Tawara, J. Am. Chem. Soc , 1971 , 93, 2573). There have, however, been no investigations of their properties as ionic liquids, and no viscosity data is available for any triaminocyclopropenium salt.

Triaminocyclopropenium salts are particularly stable due to a combination of the aromaticity of the three- membered ring and τ donation from the three planar amino groups which consequently disperse the charge from the C ₃ ring. These cations are sufficiently electron rich to be considered as "donor" species.

Accordingly, it is an object of the present invention to provide triaminocyclopropenium salts that are preferably suitable for use as ionic liquids; and/or to at least provide the public with a useful choice.

Other objects of the invention may become apparent from the following description which is given by way of example only. Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date. SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a compound of formula [Y^ _q PC ^" ] wherein q is 1, 2 or 3; and

wherein the cation, Y ^* , is a triamino l formula (I):

wherein

R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Cuo alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C ₂ _ ₂ o alkenyl, C ₂ . ₂ o alkynyl, substituted C ₂ . ₂ o alkynyl, C3.10 cycloalkyl, substituted C _3- i ₀ cycloalkyl, C3.10 cycloalkenyl, substituted C3_io cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂₀ alkyl, substituted C^o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C ₂ _ ₂₀ alkynyl, substituted C ₂ . ₂ o alkynyl, C _3- i ₀ cycloalkyl, substituted C3.10 cycloalkyl, C3.10 cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or

one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a heterocyclyl, substituted heterocyclyl, heteroaryl or substituted heteroaryl, wherein heteroaryl is imidazolyl, pyrazolyl, pyrrolyl or azepinyl; and

wherein the anion, X ^q~ , is selected from the group consisting of:

F ^" , Br ^" Γ, [I ₃ ]-, [HF ₂ ]-, [CN] ^" [SCNf, [NCO] ^" , [CH ₃ C(0)0] ^" , [(C ₂ . ₆ alkyl)C(0)0] ^" ,

[NH ₂ -CH(R ^A )C(0)0] [SiF ₆ ] ² - [S0 ₄ ] ^2" [Ν0 ₃ Γ, [C0 ₃ ] ^2" , [BPiy, [AsF ₆ ] ^" , [SbF ₆ ] ^~ , [A1C ] ^" , [A1 ₂ C1 ₇ ]- [Gad,]-, [SOeF]-, [PFgf, [A1F ₄ ]- [A1F ₆ ] ³ -, [CuCy, [SnClj] ^" , [GeCy, [ZnCL,] ^" [FeCl,] ^" , [FeC ] ^2" , [C0CI ₄ ] ^" , [CoC ] ^2" , and [Co(CO) ₄ ] ^" ;

wherein R ^A is a side chain of a natural or non-natural alpha-amino acid;

[CF3COO]-, [SeCN]-, [HSO4]- [H ₂ P0 ₄ ]- [(MeO)(H)P0 ₂ ]- [CF ₃ S0 ₃ ]- [CF ₃ OSO ₃ ]- [FHO(C,. ₆ alkyl)] ^" [(C ₂ alkyl)OS0 ₃ ]- [(C _M2 alkylJSOj] ^" , [C ₆ F ₅ S0 ₃ ]- [(C,_ ₁₂ alkyl)(C,. ₁₂ alkyl)P(0)0]-, [(C _M2 alkyl)(C,. ₁₂ alkyl-0)P(0)0] ^' , [(C,. _I2 alkyl-0)(C _M2 alkyl-0)P(0)0]-, [CH ₃ C ₆ H ₄ S0 ₃ ] ^" , [C ₁₂ H ₂₅ C ₆ H4S0 ₃ ] ^" , [CH ₂ (COO) ₂ ] ^2" , [Co(C ₂ B ₉ H„) ₂ ]-, [C ₂ B ₉ H ₁₂ ] ^" [B ₁₀ C1 ₁₀ ] ^2' , [B ₁₂ C1 ₁₂ ] ² - [CB„H ₁₂ ]- [Bi ₂ HiiN(Ci_ ₆ alkyl) ₃ ]-, [(C,. ₆ alkyl)SnBnH _u ]- [R ^B CB _U R ^C ₅ X ^B 6] ^" , and [R°BF ₃ ] ^" ;

wherein R ^B is H, Ci_6 alkyl, Ci_ ₆ alkenyl, Ci_6 perfluoroalkyl, Ci_ ₆ perfluoroalkenyl or Si(C _]-6 alkyl) ₃ ; R ^c is H, methyl, CI or Br;

R is Ci_ ₂₀ alkyl or C ₂ _ ₂ o alkenyl, wherein one or two non-adjacent carbon atoms in R ^D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein R ^D is optionally substituted by one or more R ^E ; or

R ^D is C ₃ _io cycloalkyl, C ₃ _io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Ci_ ₆ alkyl, C ₂ -6 alkenyl, and R ^E ;

R ^E at each instance is independently selected from halo, cyano, Q_6 alkoxy, Si(Cj_6 alkyl) ₃ , C ₃ _io cycloalkyl optionally substituted by one or more R ^H* , C ₃ _i ₀ cycloalkenyl optionally substituted by one or more R ^E* , aryl optionally substituted by one or more R ^E* , heteroaryl optionally substituted by one or more R ^E* , and heterocyclyl optionally substituted by one or more R ^E* ;

R ^E* at each instance is independently selected from halo, d_6 alkyl, Ci_ ₆ alkoxy, and oxycarbonyl;

X ^B is CI or Br;

[Al(OCH ₂ R ^F ) ₄ r, [(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ ] ^" [(FS0 ₂ ) ₂ N]-, [R ^F CF ₂ S0 ₃ ]- [R ^F CF ₂ OS0 ₃ ] ^~

[(R ^G S0 ₂ ) ₂ N)] - [(R ^G S0 ₂ ) ₃ C]- [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C] ^" , [R ^F CF ₂ C(0)0]\ [P(C _n F _2n+1 _ _m H _m ) _y F ₆ . _y ]- [P(C ₆ F ₅ ) _y F ₆ . _y ]-, [R ^F ₂ P(0)0]-, [R ^F P(0)0 ₂ ] ² -, [(R ^F 0) ₂ P(0)0] ^" , [(R ^F 0)(R ^F )P(0)0] ^" , [(R ^F 0)P(0)0 ₂ ] ^2"

[BF _Z R ^F 4. _Z ]-, [BF _Z (CN) ₄ . _Z ]- [Me ₃ SiC ₂ H ₄ OCH ₂ BF ₃ ]-, [N(CF ₃ ) ₂ ] ^" , [N(CN) ₂ ] ^" [C(CN) ₃ ] ^" and

. . _. J

wherein R ^F at each instance is independently selected from perfluoro Ci_ ₂₀ alkyl, perfluoro C ₂ _ ₂₀ alkenyl having one or more double bonds, perfluoro C ₂ . ₂ o alkynyl having one or more triple bonds, perfluoro C ₃ _i ₀ cycloalkyl optionally substituted by one or more perfluoro Q.6 alkyl, perfluoro C ₃ .i ₀ cycloalkenyl optionally substituted by one or more perfluoro Ci_ ₆ alkyl, and perfluorophenyl optionally substituted by one or more perfluoro C _]-6 alkyl, wherein any two R ^F may be connected by a single or double bond, wherein when R ^F is perfluoro C^o alkyl, perfluoro C ₂ _ ₂ o alkenyl, or perfluoro C ₂ _ ₂₀ alkynyl one or two non-adjacent carbon atoms in R ^F which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein a terminal carbon atom in R ^F if present, may be replaced by -S0 ₂ X ^D ; and

R ^G at each instance is independently selected from perfluoro C ₂ _ ₂₀ alkyl, perfluoro C ₂ _ ₂ o alkenyl having one or more double bonds, perfluoro C ₂ . ₂₀ alkynyl having one or more triple bonds, perfluoro C ₃ _i ₀ cycloalkyl optionally substituted by one or more perfluoro Ci _-6 alkyl, perfluoro C ₃ .i ₀ cycloalkenyl optionally substituted by one or more perfluoro Cj.6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_ ₆ alkyl, wherein any two R ^G may be connected by a single or double bond, wherein when R ^G is perfluoro C1.20 alkyl, perfluoro C2-20 alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms in R ^G which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NR ^J -, and wherein a terminal carbon atom in R ^G , if present, may be replaced by -S0 ₂ X ^D ;

R ^J at each instance is independently selected from Ci_ ₆ alkyl, fluoro Ci _-6 alkyl, perfluoro Ci_ ₆ alkyl, C3.10 cycloalkyl, phenyl optionally substituted by one or more R ^K , heteroaryl optionally substituted by one or more R ^K , and heterocyclyl optionally substituted by one or more R ^K ;

R ^K at each instance is independently selected from Ci_ ₆ alkyl, Ci-6 alkenyl, nitro, halo, hydroxyl, Ci-e alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

trifluoromethylsulfonyl, Ci_ ₆ alkoxycarbonyl, -NH ₂ , C]. ₆ alkylamino, di(Ci_ ₆

alkyl)amino, -C0 ₂ H, -C(0)NR ^L , -S0 ₂ OR ^L , -S0 ₂ X ^D , -S0 ₂ NR ^L ₂ , -S0 ₃ H, and -NHC(0)R ^L ;

R ^L at each instance is independently selected from Ci_ ₆ alkyl, fluoro Ci _-6 alkyl, perfluoro Ci_ ₆ alkyl, and C3.10 cycloalkyl;

X ^D at each instance is independently selected from F, CI, and Br;

n is 1 to 20;

m is 0, 1, 2, or 3;

y is 1 , 2, 3, or 4; and

z is 0, 1, 2, or 3; and

-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH ₂ ) ₄ C(0)-, -C(0)(CF ₂ ) _q C(0)- wherein q = l, 2 or 3, -C(CF ₃ ) ₂ C(CF ₃ ) ₂ -,

k is 1, 2, 3, or 4; and p is 1 , or 2.

In a second aspect, the present invention provides a compound of formula [Υ^ _ς Γ ^1" ] wherein q is 1 ; wherein the cation, Y\ is selected from

tris(dipropylamino)cyclopropenium,

tris(dibutylamino)cyclopropenium,

tris(dipentylamino)cyclopropenium,

tris(dihexylamino)cyclopropenium,

tris(didecylamino)cyclopropenium,

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(hexylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(diwo-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)dipropylaminocyclopropenium,

bis(diethylamino)diwo-propylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium,

bis(diethylamino)hexylmethylaminocyclopropenium,

bis(diethylamino)octadecylmethylaminocyclopropenium,

bis(diethylamino)dimethylaminocyclopropenium, and

bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium; and

wherein the anion, X ^q~ is selected from CT, Br ^" , [BF ₄ ] ^~ , [N0 ₃ ] ^" , {PF ₆ Y, [SCN] ^" , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ]- [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ]-.

In a third aspect, the present invention provides a compound of formula [Y^tX" ^1" ] wherein q is 1 ;

wherein the cation, Y is tris(diethylamino)cyclopropenium; and

wherein the anion, X ^q~ , is selected from Γ, [BF ₄ ] ^~ [N0 ₃ ] ^_ , [PF ₆ ] ^" , [SCNf, [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^"

[C ₂ H ₅ OS0 ₃ ] - [CeFsSO,] ^" , [CH ₃ C ₆ H ₄ S0 ₃ ] [(CF ₃ S0 ₂ ) ₂ N] , [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)] and [N(CN) ₂ ]-.

In a fourth aspect, the present invention provides a compound of formula [Y ^f ] _q [X ^q ] wherein q is 1 ;

wherein the cation, Y ^1" , is selected from

bis(diethylamino)aminocyclopropenium,

bis(diethylamino)butylaminocyclopropenium, bis(diethylamino)hexylaminocyclopropenium,

bis(diethylamino)diethanolaminocyclopropenium,

tris(diethanolamino)cyclopropenium,

trisanilinocyclopropenium,

bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium,

bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropeniuni ,

bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropeniuni, and

bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino))cyclopropenium; and

wherein the anion, X ^q" , is selected from [BF ₄ ] ^~ , [PF ₆ ] ^" , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ]- [C ₂ H ₅ OS0 ₃ ]\

[CH ₃ C ₆ H ₄ S0 ₃ r, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ Nr, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)r and [N(CN) ₂ ]

In a fifth aspect, the present invention provides a compound of formula [Y ⁺ ] _q [X ^q~ ] wherein q is 1 or 2 wherein the cation, Y\ is a triaminocyclopropenium ion of the formula (II):

wherein the anion, X ^q~ , is selected from [SCN] ^{^} , [CF ₃ S0 ₃ ] ^" , [FHO(C _1-6 alkyl)]-, [(C,. ₆ alkyl)OS0 ₃ ]- [C ₆ F ₅ S0 ₃ ]- [(C _1-6 alkyl)(C,. ₆ alkyl)P(0)0]-, [CH ₃ C ₆ H ₄ S0 ₃ r, [Co(C ₂ B ₉ H _u ) ₂ r, [C ₂ B ₉ H _I2 ]-, [B ₁₀ C1 ₁₀ ] ² - [B ₁₂ C1 ₁₂ ] ² -, [CB _u H ₁₂ r, [B ₁₂ H„N(C,. ₆ alkyl) ₃ r, [(C _1-6 alkyl)SnBnH _u r, [R ^B CB„R ^c ₅ X ^B 6r, [R°BF ₃ ] ^" , [(CF ₃ S0 ₂ ) ₂ N]- [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N] ^" , [R ^F CF ₂ S0 ₃ ] ^" [(R ^G S0 ₂ ) ₂ N)]- [(R ^G S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]-, [R ^F CF ₂ C(0)0]-, [P(C _n F _2n+1 . _m H _m ) _y F ₆ . _y ]- [P(C ₆ F ₅ ) _y F ₆ . -, [R ^F ₂ P(0)0]-, [R ^F P(0)0 ₂ ] ^2"

[BF _Z R ^F 4. _Z ]-, [BF _z (CN) ₄ . _z r, [N(CF ₃ ) ₂ ]-, [N(CN) ₂ ] ^" , [C(CN) ₃ r and j ; and wherein R ^B , R ^c , R ^D , X ^B , R ^F , R ^G , n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.

In a sixth aspect, the present invention provides a compound of formula wherein q is 1 or 2 wherein the cation, Y ^-1" , is a triaminocyclopropenium ion of the formula (III):

wherein R ^? is methyl and R ⁸ is selected from C2-20 alkyl, substituted C 1.20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C ₂ _ ₂ o alkynyl, substituted C2-20 alkynyl, C3.10 cycloalkyl, substituted C3 _{- ] 0} cycloalkyl, C ₃ .i ₀ cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or

R ⁷ and R ⁸ are each independently selected from C2-20 alkyl, substituted C1.20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3-10 cycloalkyl, substituted C3-10 cycloalkyl, C3.10 cycloalkenyl, substituted C ₃ .io cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;

wherein the anion, X ^{q ~} is selected from [SCNf, [CF ₃ COO] ^" , [SeCNf, [CF ₃ S0 ₃ ] ^" , [FHO(d-6 alkyl)] ^" , [(C,_6 alkyI)OS0 ₃ ]-, [C^SO,] ^" [(C,. ₆ alkyl)(C _1-6 alkyl)P(0)0]-, [CI^C^SO^, [Co(C ₂ B ₉ H _n )2] ^" , [C ₂ B ₉ H ₁₂ r, tB,oCl ₁₀ ] ² [B ₁₂ C1 ₁₂ ] ² - [CB„H ₁₂ r, [Bi2H _n N(Ci- ₆ alkyl) ₃ ] ^" , [(C,. ₆ alkyl)SnB„H„r,

[R ^B CB„R ^c ₅ X ^B 6r, [R ^D BF ₃ ] ^~ , [(CF ₃ S0 ₂ )2N]- [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N]-, [R ^F CF ₂ S0 ₃ ]-,

[(R ^G S0 ₂ ) ₂ N)]- [(R ^G S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]- [R ^F CF ₂ C(0)0]-, [P(C _n F ₂ „ ₊₁ . _m H _m ) _y F ₆ . _y ]- [P(C ₆ F ₅ ) _y F ₆ . _y ]-, [R ^F P(0)0] ^{^} , [R ^F P(0)0 ₂ ] ² - [BF _Z R ^F 4. _Z ]-, [BF _Z (CN) ₄ - _Z ]-, [N(CF ₃ ) ₂ ]-, [N(CN) ₂ ] ^~ , [C(CN) ₃ ]- and

wherein R ^B , R ^c , R ^D , X ^B , R ^F , R ^G , n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.

In a seventh aspect, the present invention provides a compound selected from the group consisting of: (2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium >-toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate; (Π) tris(dipropylamino)cyclopropenium chloride;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(18) tris(dibutylamino)cyclopropenium chloride;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(26) tris(diethanolamino)cyclopropenium fluoride;

(27) tris(diallylamino)cyclopropenium chloride;

(28) tris(diallylamino)cyclopropenium bromide;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate;

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;

(67) tris(dipentylamino)cyclopropenium chloride;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(69) tris(dipentylamino)cyclopropenium dicyanoamide;

(70) tris(dihexylamino)cyclopropenium chloride;

(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide;

(73) tris(didecylamino)cyclopropenium chloride;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;

(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;

(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(80) bis(diethylamino)aminocyclopropenium methylsulfate;

(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;

(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide; (86) bis(diethylamino)dihexylaminocyclopropenium iodide;

(87) tris(dimethylamino)cyclopropenium dicyanoamide;

(88) tris(dimethylamino)cyclopropenium thiocyanate;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;

(91) tris(dihexylamino)cyclopropenium dibutylphosphate;

(92) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;

(96) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;

(98) bis(diethylamino)-S-(l-carboxy-2-hydroxylpropylamino))cyclop ropenium

bis(trifluoromethanesulfonyl)amide;

(99) tris(dibutylamino)cyclopropenium isocyanate;

(100) tris(dibutylamino)cyclopropenium trichlorostannate;

(101 ) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;

( 102) bis(diethylamino)diwo-propylaminocyclopropenium methylsulfate;

(103) bis(diethylamino)dii5o-propylaminocyclopropenium dicyanoamide;

(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

( 107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In an eighth aspect, the present invention provides an ionic liquid comprising a triaminocyclopropenium cation and an anion.

In a ninth aspect, the present invention provides an ionic liquid comprising a compound of the invention.

In a tenth aspect, the present invention provides use of a compound of the invention as a solvent.

In an eleventh aspect, the present invention provides use of a compound of the invention as an electrolyte.

In a twelfth aspect, the present invention provides use of a compound of the invention for gas storage.

This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.

The compounds of the invention may form or exist as hydrates or solvates with various solvents. The present invention contemplates such hydrates and solvates as well as the corresponding unsolvated forms. In some embodiments, when used as ionic liquids, the compounds of the invention are unsolvated and, in particular, unhydrated.

Some of the compounds of the invention include cations or anions or both that have asymmetric carbon atoms. Therefore, stereoisomers (both enantiomers and diastereomers) of such cations or anions can exist. The present invention contemplates the pure stereoisomers (including geometric isomers) and any mixture of the isomers. For example, a pure enantiomer of a cation can be isolated from a mixture of enantiomers of the cation using conventional optical resolution techniques. Enol forms and tautomers are also contemplated, where appropriate.

It is intended that reference to a range of numbers disclosed herein (for example, 1 to 10) also

incorporates reference to all rational numbers within that range (for example, 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9 and 10) and also any range of rational numbers within that range (for example, 2 to 8, 1.5 to 5.5 and 3.1 to 4.7) and, therefore, all sub-ranges of all ranges expressly disclosed herein are hereby expressly disclosed. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. Although the present invention is broadly as defined above, those persons skilled in the art will appreciate that the invention is not limited thereto and that the invention also includes embodiments of which the following description gives examples.

DETAILED DESCRIPTION OF THE INVENTION

Definitions The term "comprising" as used in this specification means "consisting at least in part of. When interpreting each statement in this specification that includes the term "comprising", features other than that or those prefaced by the term may also be present. Related terms such as "comprise" and

"comprises" are to be interpreted in the same manner.

As used herein, the term "and/or" means "and" or "or", or both.

The general chemical terms used in the formulae herein have their usual meanings. As used herein, and unless otherwise stated: the terra "alkyl" alone or in combination with other terms means a straight chain or branched chain saturated hydrocarbon group. In some embodiments, alkyl groups comprise 1 to 20 carbon atoms. In some embodiments, alkyl groups comprise 1 to 6 carbon atoms. In some embodiments, the alkyl group is methyl, ethyl, w-propyl, wopropyl, n-butyl, wo-butyl, sec-butyl, or tert-butyl; the term "substituted alkyl" alone or in combination with other terms means an alkyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl,

cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "cycloalkyl" alone or in combination with other terms means a cyclic saturated hydrocarbon group. In some embodiments, cycloalkyl groups comprise 3 to 10 ring carbon atoms. In some embodiments, cycloalkyl groups comprise 3 to 8 ring carbon atoms. In some embodiments, the cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; the term "substituted cycloalkyl" alone or in combination with other terms means a cycloalkyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted

cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted carboxyl, oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "alkenyl" alone or in combination with other terms means a straight chain or branched chain unsaturated hydrocarbon group including at least one carbon-carbon double bond. In some embodiments, alkenyl groups comprise 2 to 20 carbon atoms. In some embodiments, alkenyl groups comprise 2 to 6 carbon atoms. In some embodiments, the alkenyl group is vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl- 1-propenyl, 2-methyl-2-propenyl, 1 -methyl- 1 -propenyl, 1 -methyl-2-propenyl, 1 -methyl vinyl, 1 -ethyl vinyl, or 1,3-butadienyl; the term "substituted alkenyl" alone or in combination with other terms means an alkenyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyloxy, cycloalkenyl,

cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "cycloalkenyl" alone or in combination with other terms means a cyclic unsaturated hydrocarbon group including at least one carbon-carbon double bond. In some embodiments, cycloalkenyl groups comprise 3 to 20 ring carbon atoms. In some embodiments, cycloalkenyl groups comprise 3 to 8 carbon atoms. In some embodiments, the cycloalkenyl group is cyclopropen-l-yl, cyclopropen-3-yl, cyclobuten- 1-yl, cyclobuten-3-yl, cyclohexen-l-yl, cyclohexen-3-yl, cyclohexen-4-yl, 1 ,3-cyclooctadien-l-yl, l ,3-cyclooctadien-2-yl, l ,3-cyclooctadien-5-yl, l,3-cyclooctadien-6-yl, 1,5-cyclooctadien-l-yl, or 1 ,5-cyclooctadien-3-yl; the term "substituted cycloalkenyl" alone or in combination with other terms means a cycloalkenyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "alkynyl" alone or in combination with other terms means a straight chain or branched chain hydrocarbon group including at least one carbon-carbon triple bond. In some embodiments, alkynyl groups comprise 2 to 20 carbon atoms. In some embodiments, alkynyl groups comprise 2 to 6 carbon atoms. In some embodiments, the alkynyl group is ethynyl, propargyl, 3-butynyl, 4-pentynyl, 5-hexynyl, or 3,5-hexadiynyl; the term "substituted alkynyl" alone or in combination with other terms means an alkynyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "alkoxy" alone or in combination with other terms means an alkyl-O- group; the term "substituted alkoxy" alone or in combination with other terms means a substituted

alkyl-O- group, wherein "substituted alkyl" is as defined herein; the term "cycloalkoxy" alone or in combination with other terms means a cycloalkyl-O- group; the term "substituted cycloalkoxy" alone or in combination with other terms means a substituted cycloalkyl-O- group, wherein "substituted cycloalkyl" is as defined herein; the term "alkenyloxy" alone or in combination with other terms means an alkenyl-O- group, wherein "alkenyl" is as defined herein; the term "substituted alkenyloxy" alone or in combination with other terms means a substituted alkenyl-O- group, wherein "substituted alkenyl" is as defined herein; the term "cycloalkenyloxy" alone or in combination with other terms means a cycloalkenyl-O- group, wherein "cycloalkenyl" is as defined herein; the term "substituted cycloalkenyloxy" alone or in combination with other terms means a substituted cycloalkenyl-O- group, wherein "substituted cycloalkenyl" is as defined herein; the term "alkynyloxy" alone or in combination with other terms means a alkynyl-O- group, wherein "alkynyl" is as defined herein; the term "substituted alkynyloxy" alone or in combination with other terms means a substituted alkynyl-O- group, wherein "substituted alkynyl" is as defined herein; the term "aryl" alone or in combination with other terms means a monocylic, bicyclic or tricyclic aromatic radical comprising only carbon and hydrogen atoms and 4 to 18 ring carbon atoms. In some embodiments, aryl is phenyl, naphthyl, indanyl, biphenyl, anthracenyl, phenanthryl, or terphenyl, and the like. In some embodiments, aryl is phenyl, naphthyl, anthracenyl, phenanthryl, biphenyl, or terphenyl. In some embodiments, aryl is phenyl, naphthyl, biphenyl, or terphenyl. In some embodiments, aryl is phenyl; the term "substituted aryl" alone or in combination with other terms means, unless otherwise stated, an aryl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted

cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryloxy, substituted

heterocyclyl, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "amino" alone or in combination with other terms means a - ^{101 102} group, wherein R ¹⁰¹ and R ¹⁰² are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted amino" alone or in combination with other terms means a -NR ¹⁰³ R ¹⁰⁴ group, wherein R ¹⁰³ and R ¹⁰⁴ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that least one of R ¹⁰³ and R ¹⁰⁴ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "amido" alone or in combination with other terms means an amino-C(O)- group; the term "substituted amido" alone or in combination with other terms means a substituted

amino-C(O)- group, wherein "substituted amino" is as defined herein; the term "acylamino" alone or in combination with other terms means an acyl-NR ¹⁰⁵ - group, wherein R ¹⁰⁵ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted acylamino" alone or in combination with other terms means a substituted acyl-NR ¹⁰⁶ - group or acyl-NR ¹⁰⁷ - group, wherein "substituted acyl" is as defined herein, R ¹⁰⁶ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R ¹⁰⁷ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "thioamide" alone or in combination with other terms means an amino-C(S)- group or

R ¹⁰⁸ C(S)NR ¹⁰⁹ - group, wherein R ¹⁰⁸ is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl and R ¹⁰⁹ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted thioamide" alone or in combination with other terms means a substituted amino-C(S)- group or R ^{1 10} C(S)NR ^{n i} - group, wherein "substituted amino" is as defined herein, R ¹¹⁰ is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R ¹¹¹ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹¹⁰ and R ⁿⁱ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "thioester" alone or in combination with other terms means a R ¹¹² SC(0)- group or

R ^U3 C(0)S- group, wherein R ¹¹² is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl, and R ¹¹³ is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted thioester" alone or in combination with other terms means a R ¹¹⁴ SC(0)- group or R ¹¹⁵ C(0)S- group, wherein R ¹¹⁴ and R ¹¹⁵ are each independently selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "carbamate" alone or in combination with other terms means an amino-C(0)0- group or oxycarbonyl-NR ¹¹⁶ - group, wherein R ¹¹⁶ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted carbamate" alone or in combination with other terms means a substituted amino-C(0)0- group, substituted oxycarbonyl-NR ¹¹⁷ - group, or oxycarbonyl-NR ¹¹⁸ - group, wherein "substituted amino" and "substituted oxycarbonyl" are as defined herein, R ¹¹⁷ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R ¹¹⁸ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "urea" alone or in combination with other terms means an amino-C(0)NR ¹¹⁹ - group, wherein R ¹¹⁹ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted urea" alone or in combination with other terms means a substituted

amino-C(0)NR ¹²⁰ - group or amino-C(0)NR ¹²¹ - group, wherein "substituted amino" is as defined herein, and R ¹²⁰ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R ¹²¹ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "dithiocarbamate" alone or in combination with other terms means an amino-C(S)S- group or R SC(S)NR - group, wherein R and R are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted dithiocarbamate" alone or in combination with other terms means a substituted amino-C(S)S- group or R ¹²⁴ SC(S)NR ¹²⁵ - group, wherein "substituted amino" is as defined herein, and R ¹²⁴ and R ¹²⁵ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹²⁴ and R ¹²⁵ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "dithiooxaamide" alone or in combination with other terms means an

amino-C(S)C(S)NR ¹²⁶ - group, wherein R ²⁶ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted dithiooxaamide" alone or in combination with other terms means a substituted amino-C(S)C(S)NR ¹²⁷ - group or amino-C(S)C(S)NR ¹²⁸ - group, wherein "substituted amino" is as defined herein, R ¹²⁷ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, and R ¹²⁸ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "imino" alone or in combination with other terms means a =NR group, wherein R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted imino" alone or in combination with other terms means a =NR ¹³⁰ group, wherein R ¹³⁰ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "aryloxy" alone or in combination with other terms means an aryl-O- group; the term "substituted aryloxy" alone or in combination with other terms means a substituted

aryl-O- group, wherein "substituted aryl" is as defined herein; the term "heteroaryl" alone or in combination with other terms means a monocyclic, bicyclic or tricyclic heteroaromatic radical comprising 5 to 14 ring atoms. In some embodiments, heteroaryl is pyrrolyl, furyl, thiophenyl, pyridyl, bipyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, pyrrodiazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, benzotriazolyl, benztetrazolyl, indazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl, cinnolinyl, indolizinyl, triazinyl, naphthyridinyl, phthalazinyl, pteridinyl, purinyl, oxazolopyridinyl, thiazolopyridinyl, imidazopyridinyl, furopyridinyl, thienopyridinyl, pyridopyrimidinyl, pyridopyrazinyl, pyridopyridazinyl, thienothiazolyl, thienoxazolyl, thienoimidazolyl, or phenazinyl. In some embodiments, heteroaryl is pyrrolyl, furyl, thiophenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, pyrrodiazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, or triazinyl; the term "substituted heteroaryl" alone or in combination with other terms means a heteroaryl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyl, substituted heterocyclyl, heterocyclyloxy, substituted heterocyclyloxy, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyl, substituted heterocyclyloxy, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "heteroaryloxy" alone or in combination with other terms means a heteroaryl-O- group; the term "substituted heteroaryloxy" alone or in combination with other terms means a substituted heteroaryl-O- group, wherein "substituted heteroaryl" is as defined herein; the term "heterocyclyl" alone or in combination with other terms means a monocyclic non-aromatic saturated or unsaturated heterocyclic radical comprising 3 to 7 ring atoms. In some embodiments, heterocyclyl is piperidinyl, pyrrolidinyl, piperazinyl, 1 ,4-dioxanyl, tetrahydrofuryl, tetrahydrothiophenyl, morpholinyl, or azepanyl. In some embodiments, heterocyclyl is tetrahydrofuryl or 1 ,4-dioxanyl; the term "substituted heterocyclyl" alone or in combination with other terms means an heterocyclyl group as defined herein, wherein one or more hydrogen atoms in the group is replaced with one or more substituents independently selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, alkenyl, substituted alkenyl, alkenyloxy, substituted alkenyloxy, cycloalkenyl, substituted cycloalkenyl, cycloalkenyloxy, substituted cycloalkenyloxy, alkynyl, substituted alkynyl, alkynyloxy, substituted alkynyloxy, aryl, substituted aryl, aryloxy, substituted aryloxy, heterocyclyloxy, substituted

heterocyclyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, formyl, acyl, substituted acyl, carboxyl, oxycarbonyl, substituted oxycarbonyl, carbonyloxy, substituted carbonyloxy, amino, substituted amino, amido, substituted amido, acylamino, substituted acylamino, imino, substituted imino, silane, substituted silane, siloxane, substituted siloxane, sulfenyl, substituted sulfenyl, sulfonyl, substituted sulfonyl, sulfoxide, substituted sulfoxide, sulfate, substituted sulfate, sulfonate, substituted sulfonate, sulfonamide, substituted sulfonamide, phosphate, substituted phosphate, phosphonate, substituted phosphonate, phosphinate, substituted phosphinate, phosphine, substituted phosphine, phosphite, substituted phosphite, carbamate, substituted carbamate, urea, substituted urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; wherein each substituted alkyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted alkenyl, substituted alkenyloxy, substituted cycloalkenyl, substituted cycloalkenyloxy, substituted alkynyl, substituted alkynyloxy, substituted aryl, substituted aryloxy, substituted heterocyclyloxy, substituted heteroaryl, substituted heteroaryloxy, substituted acyl, substituted oxycarbonyl, substituted carbonyloxy, substituted amino, substituted amido, substituted acylamino, substituted imino, substituted silane, substituted siloxane, substituted sulfenyl, substituted sulfonyl, substituted sulfoxide, substituted sulfate, substituted sulfonate, substituted sulfonamide, substituted phosphate, substituted phosphonate, substituted phosphinate, substituted phosphine, substituted phosphite, substituted carbamate, and substituted urea is independently substituted with one or more substituents independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, cycloalkyloxy, alkenyl, alkenyloxy, cycloalkenyl, cycloalkenyloxy, alkynyl, alkynyloxy, aryl, aryloxy, heterocyclyloxy, heteroaryl, heteroaryloxy, formyl, acyl, carboxyl, oxycarbonyl, carbonyloxy, amino, amido, acylamino, imino, silane, siloxane, sulfenyl, sulfonyl, sulfoxide, sulfate, sulfonate, sulfonamide, phosphate, phosphonate, phosphinate, phosphine, phosphite, carbamate, urea, halo, oxo, nitro, nitroso, nitrile, azide, isocyanate, cyanate, thiocyanate, isothiocyanate, hydroxyl, and thiol; the term "heterocyclyloxy" alone or in combination with other terms means an heterocyclyl-O- group; the term "substituted heterocyclyloxy" alone or in combination with other terms means a substituted heterocyclyl-O- group, wherein "substituted heterocyclyl" is as defined herein; the term "acyl" alone or in combination with other terms means a -C(0)R ¹³¹ group, wherein R ¹³¹ is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted acyl" alone or in combination with other terms means a -C(0)R ¹³² group, wherein R ¹³² is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "carboxyl" alone or in combination with other terms means a -C(0)OH group; the term "oxycarbonyl" alone or in combination with other terms means a -C(0)OR ¹³³ group, wherein R ¹³³ is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted oxycarbonyl" alone or in combination with other terms means a -C(0)OR ¹³⁴ group, wherein R ¹³⁴ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "carbonyloxy" alone or in combination with other terms means a -OC(0)R ¹³⁵ group, wherein R ¹³⁵ is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted carbonyloxy" alone or in combination with other terms means a -OC(0)R ¹³⁶ group, wherein R ¹³⁶ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "halo" alone or in combination with other terms means chloro, bromo, fluoro, or iodo; the term "oxo" alone or in combination with other terms means a =0 group; the term "oxy" alone or in combination with other terms means a -O- group; the term "phosphate" alone or in combination with other terms means a -OP(0)(OR ¹³⁷ )(OR ¹³⁸ ) group, wherein R ¹³⁷ and R ¹³⁸ are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphate" alone or in combination with other terms means a -OP(0)(OR ¹³⁹ )(OR ¹⁴⁰ ) group, wherein R ¹³⁹ and R ¹⁴⁰ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹³⁹ and R ¹⁴⁰ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphinate" alone or in combination with other terms means a -OP(0)R ¹⁴¹ R ¹⁴² group or -P(0)(OR ¹⁴³ )R ¹⁴⁴ group, wherein R ¹⁴¹ , R ¹⁴² , R ¹⁴³ , and R ¹⁴⁴ are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphinate" alone or in combination with other terms means a -OP(0)R ¹⁴⁵ R ¹⁴⁶ group or -P(0)(OR ¹⁴⁷ )R ¹⁴⁸ group, wherein R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , and R ¹⁴⁸ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹⁴⁵ and R ¹⁴⁶ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl and at least one of R ¹⁴⁷ and R ¹⁴⁸ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphine" alone or in combination with other terms means a -PR ¹⁴⁹ R ¹⁵⁰ group, wherein R ¹⁴⁹ and R ¹⁵⁰ are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphine" alone or in combination with other terms means a -PR ¹⁵¹ R ¹⁵² group, wherein R ¹⁵¹ and R ¹⁵² are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹⁵¹ and R ¹⁵² is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphite" alone or in combination with other terms means a -OP(OR ¹⁵³ )(OR ¹⁵⁴ ) group, wherein R ¹⁵³ and R ¹⁵⁴ are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphite" alone or in combination with other terms means a -OP(OR ¹⁵⁵ )(OR ¹⁵⁶ ) group, wherein R ¹⁵⁵ and R ¹⁵⁶ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹⁵⁵ and R ¹⁵⁶ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphonate" alone or in combination with other terms means a -P(0)(OR ¹⁵⁷ )(OR ¹⁵⁸ ) and -OP(0)(OR ¹⁵⁹ )R ¹⁶⁰ group, wherein R ¹⁵⁷ , R ¹⁵⁸ , R ¹⁵⁹ , and R ¹⁶⁰ are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphonate" alone or in combination with other terms means

a -P(0)(OR ^16I )(OR ¹⁶² ) group or -OP(0)(OR ¹⁶³ )R ¹⁶⁴ group, wherein R ¹⁶¹ , R ¹⁶² , R ¹⁶³ , and R ¹⁶⁴ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹⁶¹ and R ¹⁶² is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl and at least one of R ¹⁶³ and R ¹⁶⁴ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "phosphine oxide" alone or in combination with other terms means a -P(0)R ^l83 R ¹⁸⁴ group, wherein R ¹⁸³ and R ¹⁸⁴ are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted phosphine oxide" alone or in combination with other terms means a -P(0)R ^,85 R ¹⁸⁶ group, wherein R ¹⁸⁵ and R ¹⁸⁶ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹⁸⁵ and R ¹⁸⁶ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "silane" alone or in combination with other terms means a -SiR ¹⁸⁷ R ¹⁸⁸ R ¹⁸⁹ group, wherein R ¹⁸⁷ , R , and R are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted silane" alone or in combination with other terms means a -SiR ^I66 R ¹⁶⁷ R ¹⁶⁸ group, wherein R ¹⁶⁶ , R ¹⁶⁷ , and R ¹⁶⁸ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl, provided that at least one of R ¹⁶⁶ , R ¹⁶⁷ , and R ¹⁶⁸ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "siloxane" alone or in combination with other terms means a -Si(0)R ¹⁶⁹ group, wherein R ¹⁶⁹ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted siloxane" alone or in combination with other terms means a -Si(0)R ¹⁷⁰ group, wherein R ¹⁷⁰ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfate" alone or in combination with other terms means a -OS(0) ₂ OR ¹⁷¹ group, wherein R ¹⁷¹ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfate" alone or in combination with other terms means a -OS(0) ₂ OR ¹⁷² group, wherein R ¹⁷² is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfenyl" alone or in combination with other terms means a -SR ¹⁷³ group, wherein R ¹⁷³ is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfenyl" alone or in combination with other terms means a -SR ¹⁹⁰ group, wherein R ¹⁹⁰ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfonyl" alone or in combination with other terms means a -S(0) ₂ R ¹⁷⁴ group, wherein R ¹⁷⁴ is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfonyl" alone or in combination with other terms means a -S(0) ₂ R ¹⁷⁵ group, wherein R ¹⁷⁵ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfonamide" alone or in combination with other terms means an amino-S(0) ₂ - group or sulfonyl-NR ¹⁷⁶ - group, wherein R ¹⁷⁶ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfonamide" alone or in combination with other terms means a substituted amino-S(0) ₂ - group, sulfonyl-NR ¹⁷⁷ - group, or substituted sulfonyl-NR ¹⁷⁸ - group, wherein "substituted amino" and "substituted sulfonyl" are as defined herein, R ¹⁷⁷ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl, and R ¹⁷⁸ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl and substituted heteroaryl; the term "sulfonate" alone or in combination with other terms means a -S(0) ₂ OR ¹⁷⁹ group, wherein R ¹⁷⁹ is selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; the term "substituted sulfonate" alone or in combination with other terms means a -S(0) ₂ OR ¹⁸⁰ group, wherein R ¹⁸⁰ is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl; the term "sulfoxide" alone or in combination with other terms means a -S(0)R ¹⁸¹ group, wherein R ¹⁸¹ is alkyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl and heteroaryl; and the term "substituted sulfoxide" alone or in combination with other terms means a -S(0)R ¹⁸² group, wherein R ¹⁸² is selected from the group consisting of substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted aryl, substituted heterocyclyl and substituted heteroaryl.

As used herein, the term "substituted" means that one or more hydrogen atoms (or halo atoms for perhalo groups, such as perfluoroalkyl, perfluoroalkenyl, perfluoroalkynyl, perfluorocycloalkyl and

perfluorophenyl) in the group indicated is replaced with one or more independently selected suitable substituents, provided that the normal valency of each atom to which the substituent/s are attached is not exceeded, and that the substitution results in a stable compound.

The term "substituted alkyl", "substituted alkenyl", "substituted alkynyl", "substituted cycloalkyl", "substituted cycloalkenyl", "substituted heterocyclyl", "substituted heteroaryl", and "substituted aryl" alone or in combination with other terms include their "halo", including "monohalo-", "dihalo-" and "polyhalo-" , including "perhalo-", equivalents.

For example, the term "haloalkyl" alone or in combination with other terms means an alkyl group as defined herein wherein one or more hydrogen atoms in the group is replaced with one or more halo. The term "haloalkyl" includes monohaloalkyl, dihaloalkyl and polyhaloalkyl, including perhaloalkyl, groups. The term "perhaloalkyl" alone or in combination with other terms means an alkyl group as defined herein wherein all hydrogen atoms in the group are replaced with one or more halo. Each "halo" in any dihaloalkyl and polyhaloalkyl group is independently selected. Examples of "haloalkyl" include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, dichlorofluoromethyl, difluoroethyl, difluoropropyl, dichloroethyl and dichloropropyl. The term "perhaloalkyl" includes "perfluoroalkyl". Examples of "perfluoroalkyl" include trifluoromethyl and pentafluoroethyl. The terms "alkyl", "alkenyl", "alkynyl", "cycloalkyl", "cycloalkenyl", "heterocyclyl", "heteroaryl", and "aryl" alone or in combination with other terms, where appropriate, also include divalent and polyvalent radicals derived from each respective group, such as alkylene (alkanediyl), alkenylene, heterocyclylene, heteroarylene, and arylene. For example, where a "heteroaryl" may be substituted with up to two substituents, the "heteroaryl" may represent a monovalent heteroaryl or a divalent heteroarylene.

As used herein, the term "side chain of a natural or non-natural alpha-amino acid" includes the group R ^A in a natural or non-natural amino acid of general formula NH ₂ -CH(R ^A )-C0 ₂ H. The term also includes, for example, side chains that link to the alpha-amino group such as the pyrrolidinyl ring of proline.

Accordingly, in some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached are -pyrrolidinyl-2-C0 ₂ H. In some embodiments, X ^q" is [pyrrolidinyl-2-COO] ^" .

As used herein, the term "natural alpha-amino acid" includes the 20 L-amino acids (or a residue thereof) which commonly comprise most polypeptides in living systems, that is: alanine (Ala); arginine (Arg); asparagine (Asn); aspartic acid (Asp); cysteine (Cys); glutamine (Gin); glutamic acid (Glu); glycine (Gly); histidine (His); isoleucine (lieu); leucine (Leu); lysine (Lys); methionine (Met); phenylalanine

(Phe); proline (Pro); serine (Ser); threonine (Thr); tryptophan (Trp); tyrosine (Tyr); and valine (Val). The term also includes rarer amino acids found in fibrous proteins (for example, 4-hydroxyproline,

5-hydroxylysine, N-methyllysine and 3-methylhistidine), and naturally occurring amino acids not found in proteins (for example, homocysteine, homoserine, citrulline, ornithine, canavanine, djenkolic acid and beta-cyanoalanine).

Natural alpha-amino acids which contain functional substituents, for example amino, carboxyl, hydroxy, mercapto, guanidyl, imidazolyl or indolyl groups in their characteristic side chains include arginine, lysine, glutamic acid, aspartic acid, tryptophan, histidine, serine, threonine, tyrosine and cysteine. When any one of R ¹ to R ⁶ in the compounds of the invention is -CH(R ^A )-C0 ₂ H, wherein R ^A is a side chain of an alpha-amino acid that includes a functional substituent, such as a side chain of one of those natural alpha-amino acids or a side chain of a non-natural alpha-amino acid, the functional substituent may optionally be protected. Similarly, the carboxyl substituent in -CH(R ^A )-C0 ₂ H may optionally be protected. Further, when one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 ₂ H, the carboxyl substituent may optionally be protected. Protecting groups may be added and removed in accordance with techniques that are well known to those persons skilled in the art. The use of protecting groups is described in, for example, P. G. M. Wuts and T. W. Greene, Greene 's Protective Groups in Organic Synthesis, 4 ^th edition, Wiley, New York, 2006 and P. J. Kocienski, Protecting Groups, 3 ^rd edition, Georg Thieme Verlag, Stuttgart, 2005.

In some embodiments, the carboxyl substituent is protected as a Ci_ ₆ alkyl ester. As used herein, the term "non-natural alpha-amino acid" includes any alpha-amino acid (or residue thereof) other than the natural amino acids listed above. Non-natural amino acids include the D-isomers of the natural L-amino acids. Non-natural amino acids also include, but are not limited to:

D-phenylalanine; norleucine; hydroxyproline; carboxyglutamic acid; and pyroglutamic acid.

The prefixes "D-" or "L-" indicate an alpha-amino acid of D- or L-configuration respectively. A "D.L-" prefix indicates a racemic mixture of amino acids of the two configurations.

Triaminocyclopropenium salts

In a first aspect, the present invention provides a compound of formula [Y^ _q PC ^" ] wherein q is 1 , 2 or 3; and

wherein the cation, Y ^1" , is a formula (I):

wherein

R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C1.20 alkyl, substituted Ci_ ₂ o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C ₂ - ₂ o alkynyl, substituted C2-20 alkynyl, C ₃ _io cycloalkyl, substituted C ₃ . _]0 cycloalkyl, C ₃ _i ₀ cycloalkenyl, substituted C3.10 cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₂₀ alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C3.10 cycloalkyl, substituted C ₃ _i ₀ cycloalkyl, C3-io cycloalkenyl, substituted C ₃ .| ₀ cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or

one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a heterocyclyl, substituted heterocyclyl, heteroaryl or substituted heteroaryl, wherein heteroaryl is imidazolyl, pyrazolyl, pyrrolyl or azepinyl; and

wherein the anion, X ^q~ , is selected from the group consisting of:

F, Br ^" I ^" [Ι ₃ Γ, [HF ₂ ] ^~ , [CN] ^" [SCN] ^" , [NCO] ^" , [CH ₃ C(0)0]-, [(C ₂ . ₆ alkyl)C(0)0]-

[NH ₂ -CH(R ^A )C(0)0]-, [SiF ₆ ] ² -, [S0 ₄ ] ^2" , [N0 ₃ ] ^~ [C0 ₃ ] ² -, [BPI1 ₄ ]-, [AsF ₆ ] ^" , [SbF ₆ ] ^" , [AIC ] ^" [A1 ₂ C1 ₇ ]- [GaCU] ^" , [S0 ₆ F]-, [PF ₆ ]-, [A1F ₄ ]-, [A1F ₆ ] ^3" [CuCl ₂ ]-, [SnCl,] ^" , [GeCl,] ^" , [ZnC ] ^" [FeC ] ^" , [FeC ] ^2" , [C0CI4] ^" , [CoCL,] ^2" , and [Co(CO) ₄ ] ^" ;

wherein R ^A is a side chain of a natural or non-natural alpha-amino acid; [CF3COO]-, [SeCN]-, [HSO ₄ ]-, [H ₂ P0 ₄ ] ^' , [(MeO)(H)P0 ₂ ]- [CF ₃ SO ₃ ]- [CF ₃ OSO ₃ ]- [FHO(C,. ₆ alkyl)]-, [(C ₂ alkyi SOjF, [(C,., ₂ alkyl)S0 ₃ ]-, [(C ₂ H ₅ ) ₂ N(CH ₂ ) ₄ S0 ₃ ;r, [C^SO^, [(C _M2 alkyl)(C,_ ₁₂

alkyl)P(0)0]-, [(C,. ₁₂ alkyl)(C _M2 alkyl-0)P(0)0]-, [(C _M2 alkyl-0)(C ₂ alkyl-0)P(0)Or,

[CH ₃ C ₆ H4S0 ₃ ] ^" , [C _l2 H ₂₅ C ₆ H ₄ S0 ₃ ] ^" , [CH ₂ (COO) ₂ ] ^2" , [Co(C ₂ B ₉ H _u ) ₂ r, [C ₂ B ₉ H ₁₂ r, [B ₁₀ C1 ₁₀ ] ² -, [B ₁₂ C1 _I2 ] ^{2 ~} , [CB„H ₁₂ ]-, [BnHuNid-e alkyljj] ^" [(C,. ₆ alkyl)SnB _u Hn] ^" , [R ^B CB„R ^C ₅ X ^B 6] ^" , and [R ^D BF ₃ ] ^~ ;

wherein R ^B is H, Ci_ ₆ alkyl, C]_ ₆ alkenyl, Ci_ ₆ perfluoroalkyl, C]_ ₆ perfluoroalkenyl or Si(Ci_ ₆ alkyl) ₃ ; R ^c is H, methyl, CI or Br;

R ^D is Ci_ ₂₀ alkyl or C ₂ _ ₂₀ alkenyl, wherein one or two non-adjacent carbon atoms in R ^D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein R ^D is optionally substituted by one or more R ^E ; or

R ^D is C ₃ _io cycloalkyl, C ₃ _i ₀ cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of C _{ . ₆ alkyl, C ₂ -6 alkenyl, and R ^E ;

R ^E at each instance is independently selected from halo, cyano, Ci_ ₆ alkoxy, Si(Ci_ ₆ alkyl) ₃ , C ₃ _i ₀ cycloalkyl optionally substituted by one or more R ^E* , C3-10 cycloalkenyl optionally substituted by one or more R ^E* , aryl optionally substituted by one or more R ^E* , heteroaryl optionally substituted by one or more R ^E* , and heterocyclyl optionally substituted by one or more R ^E *;

R ^E* at each instance is independently selected from halo, Ci_6 alkyl, Ci„ ₆ alkoxy, and oxycarbonyl;

X ^B is CI or Br;

[Al(OCH ₂ R ^F ) ₄ ]-, [(CF ₃ S0 ₂ ) ₂ N]- [(CF ₃ S0 ₂ )NC(0)CF ₃ ] ^" , [(FS0 ₂ ) ₂ N] ^" [R ^F CF ₂ S0 ₃ ] ^" , [R ^F CF ₂ OS0 ₃ ]-,

[(R ^G S0 ₂ ) ₂ N)] -, [(R ^G S0 ₂ ) ₃ Cr, [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C] ^" , [R ^F CF ₂ C(0)0] ^" , [P(C _n F _2n+1 . _m H _m ) _y F ₆ . _y y]j >

[P(C ₆ F ₅ ) _Y F ₆ _ _Y ]-, [R ^F ₂ P(0)0]-, [R ^F P(0)0 ₂ ] ² -, [(R ^F O) ₂ P(0)0] ^" [(R ^F 0)(R ^F )P(0)0] ^" [(R ^F 0)P(0)0 ₂ ] ^2"

[BF _Z R ^F ₄ . _Z ]-, [BF _Z (CN) ₄ . _Z ]-, [Me ₃ SiC ₂ H ₄ 0CH ₂ BF ₃ ]- [N(CF ₃ ) ₂ ] ^" [N(CN) ₂ ] ^" , [C(CN) ₃ ]- and wherein R ^F at each instance is independently selected from perfiuoro Ci. ₂ o alkyl, perfluoro C ₂ . ₂₀ alkenyl having one or more double bonds, perfluoro C ₂ _ ₂₀ alkynyl having one or more triple bonds, perfluoro C ₃ . ₁₀ cycloalkyl optionally substituted by one or more perfluoro Ci_6 alkyl, perfluoro C ₃ .10 cycloalkenyl optionally substituted by one or more perfluoro Ci. ₆ alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci _-6 alkyl, wherein any two R ^F may be connected by a single or double bond, wherein when R ^F is perfluoro Ci. ₀ alkyl, perfluoro C ₂ _ ₂₀ alkenyl, or perfluoro C ₂ . ₂ o alkynyl one or two non-adjacent carbon atoms in R ^F which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein a terminal carbon atom in R ^F , if present, may be replaced by -S0 ₂ X ^D ; and R ^G at each instance is independently selected from perfluoro C ₂ _2o alkyl, perfluoro C ₂ _2o alkenyl having one or more double bonds, perfluoro C ₂ _2o alkynyl having one or more triple bonds, perfluoro C3.10 cycloalkyl optionally substituted by one or more perfluoro Cue alkyl, perfluoro C ₃ . ₁₀ cycloalkenyl optionally substituted by one or more perfluoro Ci_6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci _-6 alkyl, wherein any two R ^G may be connected by a single or double bond, wherein when R ^G is perfluoro Ci_ ₂₀ alkyl, perfluoro C ₂ . ₂ o alkenyl, or perfluoro C ₂ - ₂ o alkynyl one or two non-adjacent carbon atoms in R ^G which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 ₂ -, or -NR. ¹ -, and wherein a terminal carbon atom in R ^G , if present, may be replaced by -S0 ₂ X ^D ;

R ^J at each instance is independently selected from C alkyl, fluoro Ci_ ₆ alkyl, perfluoro Ci_ ₆ alkyl, C3.10 cycloalkyl, phenyl optionally substituted by one or more R ^K , heteroaryl optionally substituted by one or more R ^K , and heterocyclyl optionally substituted by one or more R ^K ;

R ^K at each instance is independently selected from Ci_ ₆ alkyl, C 6 alkenyl, nitro, halo, hydroxyl, Ci_ ₆ alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

trifluoromethylsulfonyl, Ci- alkoxycarbonyl, -NH ₂ , Ci_ ₆ alkylamino, di(Ci_6

alkyl)amino, -C0 ₂ H, -C(0)NR ^L , -S0 ₂ OR ^L , -S0 ₂ X ^D , -S0 ₂ NR ^L ₂ , -SO3H, and -NHC(0)R ^L ;

R ^L at each instance is independently selected from Cue alkyl, fluoro C ₆ alkyl, perfluoro C _]-6 alkyl, and

C3-10 cycloalkyl;

X ^D at each instance is independently selected from F, CI, and Br;

n is 1 to 20;

m is 0, 1, 2, or 3;

y is 1, 2, 3, or 4; and

z is 0, 1, 2, or 3; and

-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH ₂ ) ₄ C(0)-, -C(0)(CF ₂ ) _q C(0)- wherein q = 1 , 2 or 3, -C(CF ₃ ) ₂ C(CF ₃ ) ₂ -,

k is 1 , 2, 3, or 4; and

p is 1 , or 2.

In some embodiments, the anion, X ^q~ , is selected from the group consisting of:

F-, Br , Γ, [Is] ^" , [HF ₂ ]-, [CN] ^" , [SCN] ^" , [NCO] ^" , [CH ₃ C(0)0]-, [(C ₂ . ₆ alkyl)C(0)0] ,

[NH ₂ -CH(R ^A )C(0)0]-, [SiF ₆ ] ² - [S0 ₄ ] ² -, [Ν0 ₃ ] ^" , [CO,] ^2" , [ΒΡη,Γ, [AsF ₆ ]-, [SbF ₆ ] ^" , [AIC ] ^" , [A1 ₂ C1 ₇ ]-, [GaC ] ^" , [SO^f, [PF ₆ ]- [A1F ₄ ]-, [A1F ₆ ] ^3" [CuCl ₂ ] ^" , [SnClj] ^" [GeCl,] ^" [ZnC ] ^" [FeCl,] ^" , [FeC ] ^2" , [CoC r, [CoC ] ^2" , and [Co(CO) ₄ ] ^" ;

wherein R ^A is a side chain of a natural or non-natural alpha-amino acid;

[CF ₃ COO]-, [SeCN]-, [HS0 ₄ ] ^~ , [H ₂ P0 ₄ ] ^" , [(MeO)(H)P0 ₂ ] ^" , [CF ₃ S0 ₃ ] ^" , [CF ₃ OS0 ₃ ] ^~ , [FHO(d_ ₆ alkyl)]-, [(C., 2 alkyl)OS0 ₃ ]- [(C _M2 alkyl)S0 ₃ ]-, [(C ₂ H ₅ ) ₂ N(CH ₂ ) ₄ S0 ₃ ]- [C^SO,] ^" , [(C _1-12 alkyl)(C _M2 alkyl)P(0)0]- [(C _M2 alkyl)(C ₂ alkyl-0)P(0)0]-, [(C,. ₁₂ alkyl-0)(C _1-12 alkyl-0)P(0)0] ^' ,

[CH ₃ C ₆ H ₄ S0 ₃ ]- [C ₁₂ H ₂₅ C ₆ H ₄ S0 ₃ ]-, [CH ₂ (COO) ₂ ] ^{2 ~} [Co(C ₂ B ₉ H„) ₂ ]- [C ₂ B ₉ H ₁₂ ] ^" [B ₁₀ C1 ₁₀ ] ² [B ₁₂ C1 ₁₂ ] ² , [CB„H ₁₂ ]-, [Bi ₂ H _u N(Ci_6 alkyl),] ^" , [(C,. ₆ alkyl)SnB„H„]- [R ^B CBuR ^c ₅ X ^B 6] ^" , and [R ^D BF ₃ ] ^_ ;

wherein R ^B is H, Ci_ ₆ alkyl, Ci_ ₆ alkenyl, Ci_6 perfluoroalkyl, Ci_6 perfluoroalkenyl or Si(Ci_ ₆ alkyl) ₃ ; R ^c is H, methyl, CI or Br;

R ^D is Ci_ ₂ o alkyl or C ₂ _ ₂₀ alkenyl, wherein one or two non-adjacent carbon atoms in R ^D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein R ^D is optionally substituted by one or more R ^E ; or

R ^D is C ₃ _io cycloalkyl, C ₃ _io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Ci-6 alkyl, C ₂ -6 alkenyl, and R ^E ;

R ^E at each instance is independently selected from halo, cyano, Cj_6 alkoxy, Si(Ci_6 alkyl) ₃ , C ₃ _ _! o cycloalkyl optionally substituted by one or more R ^E* , C ₃ _io cycloalkenyl optionally substituted by one or more R ^E* , aryl optionally substituted by one or more R ^E *, heteroaryl optionally substituted by one or more R ^E \ and heterocyclyl optionally substituted by one or more R ^E *;

R ^E* at each instance is independently selected from halo, Ci_6 alkyl, Ci_6 alkoxy, and oxycarbonyl;

X ^B is CI or Br;

[(CF ₃ S0 ₂ ) ₂ N] - [(CF ₃ S0 ₂ )NC(0)CF ₃ ]- [(FS0 ₂ ) ₂ N] , [R ^F CF ₂ S0 ₃ ]-, [R ^F CF ₂ OS0 ₃ ] ^" , [(R ^G S0 ₂ ) ₂ N)] ,

[(R ^G S0 ₂ ) ₃ C]-, [(CF ₃ S0 ₂ ) ₃ C]- [(FS0 ₂ ) ₃ C] ^" , [R ^F CF ₂ C(0)0] ^" , [P(C _n F _2n+1 . _m H _m ) _y F ₆ . _y ]-, [PCC^ ^]- [R ^F ₂ P(0)0]-, [R ^F P(0)0 ₂ ] ² - [(R ^F 0) ₂ P(0)0]-, [(R ^F 0)(R ^F )P(0)0] ^" [(R ^F 0)P(0)0 ₂ ] ² -, [BF ₂ R ^F ₄ . _Z ] , [BF _Z (CN) ₄ .J- [Me ₃ SiC ₂ H40CH ₂ BF ₃ ]-, [N(CF ₃ ) ₂ ] ^" , [N(CN) ₂ ] ^~ , [C(CN) ₃ ] ^" and wherein R ^F at each instance is independently selected from perfluoro Ci_ ₂₀ alkyl, perfluoro C ₂ _ ₂₀ alkenyl having one or more double bonds, perfluoro C ₂ . ₂ o alkynyl having one or more triple bonds, perfluoro C ₃ _io cycloalkyl optionally substituted by one or more perfluoro Ci_ ₆ alkyl, perfluoro C ₃ _io cycloalkenyl optionally substituted by one or more perfluoro Ci _-6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_6 alkyl, wherein any two R ^F may be connected by a single or double bond, wherein when R ^F is perfluoro C ₁ . ₂₀ alkyl, perfluoro C ₂ . ₀ alkenyl, or perfluoro C ₂ . ₂₀ alkynyl one or two non-adjacent carbon atoms in R ^F which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 -, or -NR ^J -, and wherein a terminal carbon atom in R ^F , if present, may be replaced by -S0 ₂ X ^D ; and

R ^G at each instance is independently selected from perfluoro C _2-20 alkyl, perfluoro C ₂ . ₂₀ alkenyl having one or more double bonds, perfluoro C ₂ . ₂ o alkynyl having one or more triple bonds, perfluoro C _3- i ₀ cycloalkyl optionally substituted by one or more perfluoro C _\ . ₆ alkyl, perfluoro C _3- i ₀ cycloalkenyl optionally substituted by one or more perfluoro Ci _-6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci _-6 alkyl, wherein any two R ^G may be connected by a single or double bond, wherein when R ^G is perfluoro Ci_ ₂₀ alkyl, perfluoro C ₂ - ₂₀ alkenyl, or perfluoro C ₂ . ₂₀ alkynyl one or two non-adjacent carbon atoms in R ^G which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein a terminal carbon atom in R°, if present, may be replaced by -S0 ₂ X ^D ;

R ^J at each instance is independently selected from Ci _-6 alkyl, fluoro Ci. ₆ alkyl, perfluoro Ci_ ₆ alkyl, C ₃ . _{] 0} cycloalkyl, phenyl optionally substituted by one or more R ^K , heteroaryl optionally substituted by one or more R , and heterocyclyl optionally substituted by one or more R ^K ;

R ^K at each instance is independently selected from Ci _-6 alkyl, Ci _-6 alkenyl, nitro, halo, hydroxyl, C]. ₆ alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

trifluoromethylsulfonyl, Ci_ ₆ alkoxycarbonyl, -NH ₂ , Ci _-6 alkylamino, di(Ci _-6

alkyl)amino, -C0 ₂ H, -C(0)NR ^L , -S0 ₂ OR ^L , -S0 ₂ X ^D , -S0 ₂ NR ^L ₂ , -S0 ₃ H, and -NHC(0)R ^L ;

R ^L at each instance is independently selected from Ci _-6 alkyl, fluoro C ₆ alkyl, perfluoro Ci _-6 alkyl, and C ₃ _io cycloalkyl;

X ^D at each instance is independently selected from F, CI, and Br;

n is 1 to 20;

m is 0, 1, 2, or 3;

y is 1, 2, 3, or 4; and

z is 0, 1, 2, or 3; and -Z- and -Y- are independently selected from -C(0)C(0 , -C(0)(CH ₂ ) ₄ C(0)-, -C(0)(CF ₂ ) _q C(0)- wherein q = 1, 2 or 3, -C(CF ₃ ) ₂ C(CF ₃ ) ₂ -,

k is 1, 2, 3, or 4; and

p is 1, or 2.

In some embodiments, the anion, X ^q , is selected from the group consisting of:

F-, Br ^" Γ, [I ₃ ]-, [HF ₂ ]- [CN] ^" , [SCNT, [NCO] ^" [CH ₃ C(0)0]- [(C ₂ . ₆ alkyl)C(0)0]- [NH ₂ -CH(R ^A )C(0)0] ^" , [SiF ₆ ] ² -, [S0 ₄ ] ^{2 ~} , [ΝΟ,Γ, [C0 ₃ ] ^2" , [BPh,] ^" [AsF ₆ ]-, [SbF ₆ ] ^" , [AICL,] ^" , [A1 ₂ C1 ₇ ]- [GaC r, [S0 ₆ F]- [PF ₆ ]- [A1F ₄ ] ^" [A1F ₆ ] ³ - [CuCy, [SnClj] ^" , [GeCl ₃ ] ^~ [ZnCl ₄ ] ^~ , [FeCl ₄ ] ^" [FeC ] ^2" , [CoCl ₄ ]-, [CoC ] ^2" , and [Co(CO) ₄ ] ^" ;

wherein R ^A is a side chain of a natural or non-natural alpha-amino acid. This group is referred to herein as "Group 1".

In some embodiments, the anion, X ^q~ , is selected from the group consisting of:

[CF ₃ COOr, [SeCN]- [HS0 ₄ ] ^" [H ₂ P0 ₄ ] ^" [(MeO)(H)P0 ₂ ] ^" [CF ₃ S0 ₃ ] ^" , [CF ₃ OS0 ₃ ] ^" , [FHO(C _1-6 alkyl)] ^" [(Ci.,2 alkyl)OS0 ₃ ]-, [(C ₂ alkyl)S0 ₃ r, [(C ₂ H ₅ ) ₂ N(CH ₂ ) ₄ S0 ₃ r, [C^SO,] ^" [(C,. ₁₂ alkyl)(C,. ₁₂ alkyl)P(0)0]-, [(C _M2 alkyl)(C _M2 alkyl-0)P(0)0]-, [(C,_ ₁₂ alkyl-0)(C,_ ₁₂ alkyl-0)P(0)Or,

[CH ₃ C ₆ H ₄ S0 ₃ ] ^" , [C ₁₂ H ₂₅ C ₆ H ₄ S0 ₃ ]-, [CH ₂ (COO) ₂ ] ^2" , [Co(C ₂ B ₉ H, ,) ₂ ] ^" , [C ₂ B ₉ H ₁₂ ]-, [B ₁₀ C1 ₁₀ ] ² - [B ₁₂ C1 ₁₂ ] ² -, [CB _n H ₁₂ ]- [Bi ₂ HiiN(Ci_6 alkyl),] ^" , [(C _1-6 alky SnBnHn] ^" [R ^B CB„R ^C ₅ X ^B ₆ ]-, and [R°BF ₃ ]-;

wherein R ^B is H, Ci_ ₆ alkyl, Ci_ ₆ alkenyl, Ci_ ₆ perfluoroalkyl, Ci_ ₆ perfluoroalkenyl or Si(Ci _-6 alkyl) ₃ ; R ^c is H, methyl, CI or Br; R ^D is C-20 alkyl or C ₂ _ ₂ o alkenyl, wherein one or two non-adjacent carbon atoms in R ^D which are not in the alpha-position may be replaced by -0-, -S-, -C(0)0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein R ^D is optionally substituted by one or more R ^E ; or

R ^D is C ₃ _io cycloalkyl, C3_io cycloalkenyl, aryl, heteroaryl, or heterocyclyl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of Q. ₆ alkyl, C ₂ - ₆ alkenyl, and R ^E ;

R ^E at each instance is independently selected from halo, cyano, C)_ ₆ alkoxy, Si(Ci_ ₆ alkyl) ₃ , C ₃ _io cycloalkyl optionally substituted by one or more R ^E* , C ₃ _i ₀ cycloalkenyl optionally substituted by one or more R ^E* , aryl optionally substituted by one or more R ^E* , heteroaryl optionally substituted by one or more R ^E* , and heterocyclyl optionally substituted by one or more R ^E* ;

R ^E* at each instance is independently selected from halo, Ci_ ₆ alkyl, Ci_ ₆ alkoxy, and oxycarbonyl;

R ^J at each instance is independently selected from Ci _-6 alkyl, fluoro Ci_ ₆ alkyl, perfluoro Ci _-6 alkyl, C ₃ _io cycloalkyl, phenyl optionally substituted by one or more R ^K , heteroaryl optionally substituted by one or more R ^K , and heterocyclyl optionally substituted by one or more R ^K ;

R ^K at each instance is independently selected from Ci. ₆ alkyl, C]_ ₆ alkenyl, nitro, halo, hydroxyl, C]. ₆ alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

trifluoromethylsulfonyl, C _\ . ₆ alkoxycarbonyl, -NH ₂ , Ci_ ₆ alkylamino, di(Ci _-6

alkyl)amino, -C0 ₂ H, -C(0)NR ^L , -S0 ₂ OR ^L , -S0 ₂ X ^D , -S0 ₂ NR ^L ₂ , -S0 ₃ H, and -NHC(0)R ^L ;

R ^L at each instance is independently selected from Ci_ ₆ alkyl, fluoro Ci- ₆ alkyl, perfluoro Ci_e alkyl, and C ₃ .io cycloalkyl;

X ^B is CI or Br; and

X ^D at each instance is independently selected from F, CI, and Br. This group is referred to herein as

"Group 2".

In some embodiments, the anion, X ^q , is selected from the group consisting of: [Al(OCH ₂ R ^F ) ₄ ] ,

[(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ ]- [(FS0 ₂ ) ₂ N] ^~ [R ^F CF ₂ S0 ₃ ] ^" [R ^F CF ₂ OS0 ₃ ] ^~ , [(R ^G S0 ₂ ) ₂ N)] ^" ,

[(R ^G S0 ₂ ) ₃ C]-, [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]-, [R ^F CF ₂ C(0)0] ^" , [P(C _n F _2n+1 . _m H _m ) _y F ₆ . _y r, [P(C ₆ F ₅ ) _y F ₆ . _y ]- [R ^F ₂ P(0)0]- [R ^F P(0)0 ₂ ] ² -, [(R ^F 0) ₂ P(0)0]- [(R ^F 0)(R ^F )P(0)0] ^' , [(R ^F O)P(0)0 ₂ ] ^2" , [BF _Z R ^F _4-Z ]-,

[BF _z (CN) ₄ -z] [Me ₃ SiC ₂ H ₄ OCH ₂ BF ₃ r, [N(CF ₃ ) ₂ ]-, [N(CN) ₂ ] ^" , [C(CN) ₃ ] ^" and

one or more perfluoro Ci _-6 alkyl, wherein any two R ^F may be connected by a single or double bond, wherein when R ^F is perfluoro Ci_ ₂₀ alkyl, perfluoro C ₂ . ₂₀ alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NR ^J -, and wherein a terminal carbon atom in R ^F , if present, may be replaced by -S0 ₂ X ^D ; and

R ^G at each instance is independently selected from perfluoro C2-20 alkyl, perfluoro C2-20 alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro C3.10 cycloalkyl optionally substituted by one or more perfluoro Ci-e alkyl, perfluoro C3.10 cycloalkenyl optionally substituted by one or more perfluoro C _t . ₆ alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci.6 alkyl, wherein any two R ^G may be connected by a single or double bond, wherein when R ^G is perfluoro Ci_ ₂ o alkyl, perfluoro C ₂ _ ₂₀ alkenyl, or perfluoro C2-20 alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO2-, or -NR ^J -, and wherein a terminal carbon atom in R ^G , if present, may be replaced by -S0 ₂ X ^D ;

R ^J at each instance is independently selected from Ci _-6 alkyl, fluoro d. ₆ alkyl, perfluoro Ci _-6 alkyl, C ₃ _i ₀ cycloalkyl, phenyl optionally substituted by one or more R ^K , heteroaryl optionally substituted by one or more R ^K , and heterocyclyl optionally substituted by one or more R ;

R ^K at each instance is independently selected from Ci.6 alkyl, Ci _-6 alkenyl, nitro, halo, hydroxyl, Ci. ₆ alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

trifluoromethylsulfonyl, Ci_ ₆ alkoxycarbonyl, -NH ₂ , Ci _-6 alkylamino, di(C]. ₆

alkyl)amino, -C0 ₂ H, -C(0)NR ^L , -S0 ₂ OR ^L , -S0 ₂ X ^D , -S0 ₂ NR ^L ₂ , -S0 ₃ H, and -NHC(0)R ^L ;

R ^L at each instance is independently selected from C]. ₆ alkyl, fluoro Ci-6 alkyl, perfluoro Ci. ₆ alkyl, and

C3.10 cycloalkyl;

X ^D at each instance is independently selected from F, CI, and Br;

n is 1 to 20;

m is 0, 1, 2, or 3;

y is 1, 2, 3, or 4; and

z is 0, 1, 2, or 3; and

-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH ₂ ) ₄ C(0)-, -C(0)(CF ₂ ) _q C(0)- wherein q = 1, 2 or 3, -C(CF ₃ ) ₂ C(CF ₃ ) ₂ -,

k is 1 , 2, 3, or 4; and

p is 1 , or 2. This group is referred to herein as "Group 3".

In some embodiments, the Group 3 anion, X ^q , is selected from the group consisting of: [(CF ₃ S02)2N] ^~ , [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N]- [R ^F CF ₂ S0 ₃ j-, [R ^F CF ₂ OS0 ₃ ]-, [(R ^G S0 ₂ ) ₂ N)]-, [(R ^G S0 ₂ ) ₃ Cr,

[(CF ₃ S0 ₂ ) ₃ Cr, [(FS0 ₂ ) ₃ C] - [R ^F ₂ P(0)0] ^"

[R ^F P(0)0 ₂ ] ² -, [(R ^F 0) ₂ P(0)Or, [(R ^F 0)(R ^F )P(0)0]-, [(R ^F 0)P(0)0 ₂ ] ² -, [BF _Z R ^F ₄ .J- [BF _Z (CN) ₄ . _Z ]-

[Me ₃ SiC ₂ H ₄ OCH ₂ BF ₃ ] ^~ [N(CF ₃ ) ₂ ] ^" , [N(CN) ₂ ] , [C(CN) ₃ r and

wherein R ^F at each instance is independently selected from perfluoro Ci_ ₂ o alkyl, perfluoro C ₂ -2o alkenyl having one or more double bonds, perfluoro C2- ₂ o alkynyl having one or more triple bonds, perfluoro C ₃ _i ₀ cycloalkyl optionally substituted by one or more perfluoro Cj.6 alkyl, perfluoro C ₃ _i ₀ cycloalkenyl optionally substituted by one or more perfluoro Ci_6 alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci _-6 alkyl, wherein any two R ^F may be connected by a single or double bond, wherein when R ^F is perfluoro Ci. ₂ o alkyl, perfluoro C ₂ _2o alkenyl, or perfluoro C ₂ _ ₂ o alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -S0 ₂ -, or -NR ^J -, and wherein a terminal carbon atom in R ^F , if present, may be replaced by -S0 ₂ X ^D ; and

R ^G at each instance is independently selected from perfluoro C ₂ . ₂₀ alkyl, perfluoro C ₂ . ₂ o alkenyl having one or more double bonds, perfluoro C2-20 alkynyl having one or more triple bonds, perfluoro C ₃ _io cycloalkyl optionally substituted by one or more perfluoro Ci_ ₆ alkyl, perfluoro C ₃ .i ₀ cycloalkenyl optionally substituted by one or more perfluoro C e alkyl, and perfluorophenyl optionally substituted by one or more perfluoro Ci_ ₆ alkyl, wherein any two R ^G may be connected by a single or double bond, wherein when R ^G is perfluoro Ci_ ₂ o alkyl, perfluoro C2-20 alkenyl, or perfluoro C2-2 ₀ alkynyl one or two non-adjacent carbon atoms which are not in the alpha-position to a heteroatom may be replaced by -0-, -S(O)-, -SO ₂ -, or -NR ^J -, and wherein a terminal carbon atom in R°, if present, may be replaced by -S0 ₂ X ^D ;

R ^J at each instance is independently selected from Ci_ ₆ alkyl, fluoro Ci_ ₆ alkyl, perfluoro C _]-6 alkyl, C ₃ _io cycloalkyl, phenyl optionally substituted by one or more R ^K , heteroaryl optionally substituted by one or more R ^K , and heterocyclyl optionally substituted by one or more R ^K ;

R ^K at each instance is independently selected from Ci_6 alkyl, Ci_6 alkenyl, nitro, halo, hydroxyl, Ci_6 alkoxy, cyanate, thiocyanate, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

trifluoromethylsulfonyl, Ci _-6 alkoxycarbonyl, -NH ₂ , Ci_ ₆ alkylamino, di(Ci_ ₆

alkyl)amino, -C0 ₂ H, -C(0)NR ^L , -S0 ₂ OR ^L , -S0 ₂ X ^D , -S0 ₂ NR ^L ₂ , -SO ₃ H, and -NHC(0)R ^L ;

R ^L at each instance is independently selected from Ci.6 alkyl, fluoro Ci-6 alkyl, perfluoro Ci-e alkyl, and C3-10 cycloalkyl;

X ^D at each instance is independently selected from F, CI, and Br;

n is 1 to 20;

m is 0, 1, 2, or 3;

y is 1 , 2, 3, or 4; and

z is 0, 1, 2, or 3; and

-Z- and -Y- are independently selected from -C(0)C(0)-, -C(0)(CH ₂ ) ₄ C(0)-, -C(0)(CF ₂ ) _q C(0)- wherein q = l, 2 or 3, -C(CF3) ₂ C(CF ₃ )2-,

k is 1 , 2, 3, or 4; and

p is 1 , or 2.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C ₂ -2o alkynyl, aryl, and substituted aryl; and

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂ o alkyl, substituted Ci _-2 o alkyl, C _2-2 o alkenyl, substituted C _2-2 o alkenyl, C ₂ _ ₂₀ alkynyl, substituted C ₂ _ ₂ o alkynyl, aryl, and substituted aryl; or one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, substituted Ci_ ₂₀ alkyl, C ₂ _ ₂ o alkenyl, substituted C ₂ . ₂ o alkenyl, C _2-2 o alkynyl, and substituted C ₂ - ₂ o alkynyl; and R ⁴ and R ⁶ are each independently selected from C ₂ _ ₂ o alkyl, substituted Ci_ ₂ o alkyl, C ₂ _ ₂₀ alkenyl, substituted C ₂ . ₂ o alkenyl, C ₂ - ₂ o alkynyl, and substituted C ₂ . ₂₀ alkynyl; or

one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, substituted Ci_2o alkyl, C _2-2 o alkenyl, substituted C ₂ _ ₂₀ alkenyl, aryl, and substituted aryl; and

R ⁴ and R ⁶ are each independently selected from C ₂ - ₂ o alkyl, substituted Ci_ ₂ o alkyl, C ₂ . ₂₀ alkenyl, substituted C ₂ - ₂ o alkenyl, aryl, and substituted aryl; or

R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, substituted C]. ₂ o alkyl, C ₂ - ₂ o alkenyl, and substituted C ₂ . ₂ o alkenyl; and

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂₀ alkyl, substituted Ci_ ₂₀ alkyl, C ₂ . ₂₀ alkenyl, and substituted C _2-2 o alkenyl; or

R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci_ ₂ o alkyl, C ₂ . ₂ o alkenyl, substituted C ₂ . ₂ o alkenyl, aryl, and substituted aryl; and R ⁴ and R ⁶ are each independently selected from C ₂ .2o alkyl, substituted C^o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl. In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C1.20 alkyl, substituted Ci-20 alkyl, C ₂ . ₂ o alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₂₀ alkyl, C2-20 alkenyl, and aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-6 alkyl, C ₂ . ₆ alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂₀ alkyl, substituted alkyl, C _2- 6 alkenyl, and aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl.

In some embodiments, R ¹ , R ² and R ³ are each independently selected from -H, Ci. ₀ alkyl, substituted Ci-20 alkyl, C _2- 2o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and

R ⁴ is selected from C2-20 alkyl, substituted C1.20 alkyl, C2- ₂ o alkenyl, substituted C ₂ _ ₂₀ alkenyl, aryl, and substituted aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ² and R ³ are each independently selected from -H, Ci _-2 o alkyl, substituted Ci_ ₂₀ alkyl, C ₂ . ₂ o alkenyl, and aryl; and

R ⁴ is selected from C ₂ . ₂ o alkyl, substituted C1.20 alkyl, C ₂ . ₂ o alkenyl, and aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ² and R ³ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci_ ₆ alkyl, C2-6 alkenyl, and aryl; and

R ⁴ is selected from C ₂ . ₂₀ alkyl, substituted Ci_6 alkyl, C ₂ _6 alkenyl, and aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-20 alkyl, C _2-2 o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and R ² , R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₂ o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl. In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and aryl; and

R ² , R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₂ o alkyl, C2-20 alkenyl, and aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ and R ³ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, substituted C ₂ .2o alkenyl, aryl, and substituted aryl; and

R ² and R ⁴ are each independently selected from C2-20 alkyl, substituted C _)-2 o alkyl, C2-20 alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ and R ³ are each independently selected from -H, Ci_ ₂ o alkyl, substituted C1.20 alkyl, C2-20 alkenyl, and aryl; and

R ² and R ⁴ are each independently selected from C2-20 alkyl, substituted C _1-2 o alkyl, C2-20 alkenyl, and aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ and R ³ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci.6 alkyl, C ₂ -e alkenyl, and aryl; and

R ² and R ⁴ are each independently selected from C2-20 alkyl, substituted Ci-e alkyl, C ₂ -6 alkenyl, and aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl.

In some embodiments, R ¹ and R ³ are each independently selected from -H, Ci _-2 o alkyl, hydroxy _\ . ₆ alkyl, carboxyl C ₆ alkyl, Ci_ ₆ alkoxycarbonyl Ci_ ₆ alkyl, Ci_ ₆ alkoxy Ci _-6 alkyl, Ci_6 alkyl-NH ₂ , Ci_ ₆ alkylamino Ci_ ₆ alkyl, carboxyl hydroxy Ci_ ₆ alkyl, C ₂ _6 alkenyl, and aryl; and

R ² and R ⁴ are each independently selected from C2-20 alkyl, hydroxy Ci. ₆ alkyl, carboxyl Ci. ₆ alkyl, Ci_6 alkoxycarbonyl Ci_ ₆ alkyl, C1-5 alkoxy Ci_ ₆ alkyl, Ci_ ₆ alkyl-NH ₂ , _\ . ₆ alkylamino Ci _-6 alkyl, carboxyl hydroxy Cj.6 alkyl, C ₂ _ ₆ alkenyl, and aryl; and R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl.

In some embodiments, wherein one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl, the heterocyclyl or substituted heterocyclyl is pyrrolidinyl, substituted pyrrolidinyl, piperidinyl, substituted piperidinyl, morpholinyl, substituted morpholinyl, azepanyl, or substituted azepanyl.

In some embodiments, the heterocyclyl or substituted heterocyclyl is pyrrolidinyl or substituted pyrrolidinyl.

In some embodiments, R ¹ and R ³ are each independently selected from -H, Ci_ ₂ o alkyl, hydroxy Ci_ ₆ alkyl, carboxyl Ci _-6 alkyl, Ci_ ₆ alkoxycarbonyl Cj _-6 alkyl, Ci _-6 alkoxy Ci _-6 alkyl, Ci _-6 alkyl-NH ₂ , C _1-6 alkylamino Ci _-6 alkyl, carboxyl hydroxy Ci_6 alkyl, C ₂ _6 alkenyl, and aryl; and

R ² and R ⁴ are each independently selected from C ₂ . ₂₀ alkyl, hydroxy Ci_ ₆ alkyl, carboxyl C]. ₆ alkyl, Ci-e alkoxycarbonyl Ci _-6 alkyl, Ci_ ₆ alkoxy Ci-β alkyl, Ci _-6 alkyl-NH ₂ , Ci_ ₆ alkylamino C]. ₆ alkyl, carboxyl hydroxy C| _-6 alkyl, C ₂ _6 alkenyl, and aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a substituted pyrrolidinyl. In some embodiments, wherein one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl, the heterocyclyl is substituted by one or more carboxyl groups.

In some embodiments, wherein one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl, the heterocyclyl is substituted by one or more substituents independently selected from Cj. ₆ alkyl, C ₁ .6 alkoxy and C _a alkoxy C _b alkyl wherein a and b are independently 1 , 2, 3, 4, or 5 and the sum (a + b) is 2, 3, 4, 5, or 6.

In some embodiments, wherein one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ independently form, together with the nitrogen atom to which they are attached, a substituted heterocyclyl, the heterocyclyl is substituted by one or more substituents independently selected from Ci_ ₆ alkyl and C _a alkoxy C _b alkyl wherein a and b are independently 1 , 2, 3, 4, or 5 and the sum (a + b) is 2, 3, 4, 5, or 6.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C]_ ₂ o alkyl, substituted Cue alkyl, C _2-2 o alkenyl, substituted C ₂ . ₂₀ alkenyl, aryl, and substituted aryl; and

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂ o alkyl, substituted Cuo alkyl, C _2-20 alkenyl, substituted C ₂ _ ₂ o alkenyl, aryl, and substituted aryl. In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, substituted Ci_2o alkyl, C _2-2 o alkenyl, substituted C ₂ - ₂ o alkenyl, aryl, and substituted aryl; and R ² , R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted C i_ ₂ o alkyl, C ₂ _2o alkenyl, substituted C2-20 alkenyl, aryl, and substituted aryl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and substituted C2-20 alkenyl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₂ o alkyl, C2-20 alkenyl, and substituted C2-20 alkenyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C _t .20 alkyl, substituted Ci-20 alkyl, C2-20 alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C ₂ _2o alkyl, substituted C^o alkyl, C2-20 alkenyl, and aryl. In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, C ]. ₂ o alkyl, substituted C |.2o alkyl, and C2-20 alkenyl; and

R ² , R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted C i _-2 o alkyl, C ₂ _2o alkenyl, and aryl.

In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, C1.20 alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl;

R ² is selected from -H, Ci. ₂ o alkyl, substituted Ci_ ₂ o alkyl, C2-20 alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C ₂ _2o alkyl, substituted C^o alkyl, C2-20 alkenyl, and aryl.

In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl; and

R ² , R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci _-2 o alkyl, C2-20 alkenyl, and aryl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci-20 alkyl, and C2-20 alkenyl; and

R ⁴ and R ⁶ are each independently selected from C ₂ _2o alkyl, substituted Ci_ ₂ o alkyl, and C2-20 alkenyl. In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C1.20 alkyl, substituted Ci-6 alkyl, C ₂ -6 alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₆ alkyl, C2- alkenyl, and aryl.

In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, C1.20 alkyl, substituted Ci.« alkyl, and C _2- 6 alkenyl;

R ² is selected from -H, Ci _-2 o alkyl, substituted C,_ ₆ alkyl, C _2- 6 alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₆ alkyl, C ₂ . ₆ alkenyl, and aryl. In some embodiments, R ¹ , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci_ ₆ alkyl, and C2-6 alkenyl; and

R ² , R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci. ₆ alkyl, C ₂ . ₆ alkenyl, and aryl. In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci _-2 o alkyl, substituted Ci_6 alkyl, and C ₂ _6 alkenyl; and

R ⁴ and R ⁶ are each independently selected from C ₂ _2o alkyl, substituted C1.6 alkyl, and C ₂ -6 alkenyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C1.20 alkyl, hydroxy Ci-6 alkyl, carboxyl Ci _-6 alkyl, C _1-6 alkoxycarbonyl Ci _-6 alkyl, C _\ . ₆ alkoxy Ci_ ₆ alkyl, d _-6 alkyl-NH ₂ , Ci _-6 alkylamino Ci_ ₆ alkyl, carboxyl hydroxy Ci _-6 alkyl, C ₂ -6 alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, hydroxy Ci_ ₆ alkyl, carboxyl Ci.6 alkyl, C]_ ₆ alkoxycarbonyl Ci_ ₆ alkyl, Ci _-6 alkoxy C _\ . ₆ alkyl, C]. ₆ alkyl-NH ₂ , Ci _-6 alkylamino Ci _-6 alkyl, carboxyl hydroxy C _\ .(, alkyl, C2-6 alkenyl, and aryl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, hydroxy Ci.6 alkyl, carboxyl Ci _-6 alkyl, Ci_ ₆ alkoxycarbonyl Ci_ ₆ alkyl, C _\ . ₆ alkoxy Ci_ ₆ alkyl, C]. ₆ alkyl-NH ₂ , Ci _-6 alkylamino Ci.6 alkyl and C2-6 alkenyl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, hydroxy Ci _-6 alkyl, carboxyl Ci. ₆ alkyl, C _\ . ₆ alkoxycarbonyl Ci_ ₆ alkyl, Ci-6 alkoxy Ci_ ₆ alkyl, Ci_ ₆ alkyl-NH ₂ , Ci_ ₆ alkylamino Ci_ ₆ alkyl and C ₂ -6 alkenyl. In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, hydroxy Ci_6 alkyl, carboxyl C e alkyl, carboxyl hydroxy Ci _-6 alkyl, C ₂ _6 alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci„ ₆ alkyl, C ₂ -e alkenyl, and aryl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci _-2 o alkyl, hydroxy Ci-6 alkyl, carboxyl C _\ .e alkyl, and C ₂ -6 alkenyl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, hydroxy Ci_6 alkyl, carboxyl Ci.6 alkyl, and C ₂ -6 alkenyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C]. ₂ o alkyl, hydroxy Ci_e alkyl, and C _2-6 alkenyl; and

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, hydroxy Ci_ ₆ alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci_6 alkyl, and C ₂ -6 alkenyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, hydroxy Ci-6 alkyl, and C2-6 alkenyl; and R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, hydroxy Ci_ ₆ alkyl, carboxyl Ci. ₆ alkyl, and C2-6 alkenyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, methyl, ethyl,

H-propyl, wo-propyl, n-butyl, w-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R ⁴ and R ⁶ are each independently selected from ethyl, «-propyl, /so-propyl, n-butyl, w-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; or

R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, methyl, ethyl,

M-propyl, wo-propyl, «-butyl, «-pentyl, n-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R ⁴ and R ⁶ are each independently selected from ethyl, n-propyl, z ^' so-propyl, «-butyl, «-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, methyl, ethyl, «-propyl, «ο-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, and allyl; and

R ⁴ and R ⁶ are each independently selected from ethyl, n-propyl, wo-propyl, «-butyl, n-hexyl, stearyl, 2-hydroxyethyl, 1-carboxylethyl, and allyl.

In some embodiments, R'-R ⁶ are identical. In some embodiments, R ^] -R ⁶ are identical and are C2-20 alkyl, substituted Ci_6 alkyl, or C ₂ .e alkenyl. In some embodiments, R ^l -R ⁶ are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl. In some embodiments, R'-R ⁶ are identical and are pentyl, hexyl, or decyl. In some embodiments, R ^] -R ⁶ are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl. In some embodiments, R'-R ⁶ are identical and are 2-hydroxyethyl.

In some embodiments, wherein R'-R ⁶ are identical, each of R'-R ⁶ comprise 2- 10 non-hydrogen atoms. In some embodiments, wherein R'-R ⁶ are identical, each of R'-R ⁶ comprise 2-6 non-hydrogen atoms. In some embodiments, the anion, X ^q~ , is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.

In some embodiments, R ¹ , R ³ and R ⁵ are identical. In some embodiments, R ¹ , R ³ and R ⁵ are identical and are -H, C1.20 alkyl, substituted Ci_6 alkyl, or C ₂ -6 alkenyl. In some embodiments, R ¹ , R ³ and R ⁵ are identical and are C1.20 alkyl, substituted Ci_e alkyl, or C ₂ -6 alkenyl. In some embodiments, R ¹ , R ³ and R ⁵ are identical and are C2-20 alkyl, substituted C e alkyl, or C ₂ -6 alkenyl.

In some embodiments, R ⁴ , R ⁵ and R ⁶ are identical. In some embodiments, R ² , R ⁴ and R ⁶ are identical and are C2-20 alkyl, substituted Ci_ ₆ alkyl, C ₂ -e alkenyl, or aryl. In some embodiments, R ² , R ⁴ and R ⁶ are identical and are C2-20 alkyl, substituted Ci_ ₆ alkyl, C ₂ -6 alkenyl, or phenyl. In some embodiments, R ¹ , R ³ and R ⁵ are identical, R ² , R ⁴ and R ⁶ are identical, and R ¹ and R ² are different. In some embodiments, R ¹ , R ³ and R ⁵ are identical and are -H, Ci_ ₂ o alkyl, substituted Ci _-6 alkyl, or C ₂ -e alkenyl, and R ² , R ⁴ and R ⁶ are identical and are C2-20 alkyl, substituted Ci_6 alkyl, C2-6 alkenyl, or aryl, and R' and R ² are different. In some embodiments, R ¹ , R ³ and R ⁵ are identical and are -H, C1.20 alkyl, substituted Ci_ ₆ alkyl, or C ₂ -e alkenyl, and R ² , R ⁴ and R ⁶ are identical and are C ₂ _2o alkyl, substituted Ci_ ₆ alkyl, C2-6 alkenyl, or phenyl, and R ¹ and R ² are different. In some embodiments, R ¹ , R ³ and R ⁵ are identical and are Ci_ ₂ o alkyl, substituted Ci_ ₆ alkyl, or C ₂ -6 alkenyl, and R ² , R ⁴ and R ⁶ are identical and are C2-20 alkyl, substituted Ci_ ₆ alkyl, or C ₂ -e alkenyl, and R ¹ and R ² are different. In some embodiments, R ¹ , R ³ and R ⁵ are identical and are C2-20 alkyl, substituted Ci_ ₆ alkyl, or C ₂ -6 alkenyl, and R ² , R ⁴ and R ⁶ are identical and are C2-20 alkyl, substituted Ci_ ₆ alkyl, or C ₂ _ ₆ alkenyl, and R ¹ and R ² are different.

In some embodiments, R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl.

In some embodiments, R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl.

In some embodiments, R ¹ , R ³ and R ⁵ are -H and R ² , R ⁴ and R ⁶ are phenyl.

In some embodiments, wherein R ¹ , R ³ and R ⁵ are identical, R ² , R ⁴ and R ⁶ are identical, and R ¹ and R ² are different, R ¹ and R ² together comprise 2-10 non-hydrogen atoms. In some embodiments, R ¹ is not -H. In some embodiments, the anion, X ^q~ , is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.

In some embodiments, wherein R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl, the anion, X ^q~ , is selected from Group 3. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are identical. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are identical and are C ₂ _2o alkyl, substituted Q-e alkyl, or C ₂ _6 alkenyl.

In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical. In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical and are C ₂ - ₂ o alkyl, substituted Ci _-6 alkyl, or C ₂ -6 alkenyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are identical, R ⁵ and R ⁶ are identical, and R ¹ and R ⁵ are different. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are identical and are C ₂ _2o alkyl, substituted C _1-6 alkyl, or C _2-6 alkenyl, R ⁵ and R ⁶ are identical and are C2-20 alkyl, substituted Ci _-6 alkyl, or C _2- e alkenyl, and R ¹ and R ⁵ are different.

In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical, R ¹ and R ² are identical, and R ¹ and R ³ are different. In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical and are Ci _-2 o alkyl, substituted Ci _-6 alkyl, or C _2- alkenyl, R ¹ and R ² are identical and are -H, C _2-20 alkyl, substituted Ci_ ₆ alkyl, or C ₂ _ ₆ alkenyl, and R ¹ and R ³ are different. In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical and are Ci-20 alkyl, substituted Ci_ alkyl, or C ₂ - ₆ alkenyl, R ¹ and R ² are identical and are C ₂ _2o alkyl, substituted Ci _-6 alkyl, or C ₂ . ₆ alkenyl, and R ¹ and R ³ are different. In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical and are C2-20 alkyl, substituted Ci. ₆ alkyl, or C2-6 alkenyl, R ¹ and R ² are identical and are -H, C2-20 alkyl, substituted C _]-6 alkyl, or C ₂ . ₆ alkenyl, and R ¹ and R ³ are different. In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical and are C ₂ . ₂ o alkyl, substituted Ci_ ₆ alkyl, or C ₂ . ₆ alkenyl, R ¹ and R ² are identical and are C2-20 alkyl, substituted Ci_ ₆ alkyl, or C2-6 alkenyl, and R ¹ and R ³ are different.

In some embodiments, wherein R ¹ , R ² , R ³ and R ⁴ are identical, R ⁵ and R ⁶ are identical, and R ¹ and R ⁵ are different, R ¹ , R ² , R ³ and R ⁴ are ethyl. In some embodiments, R ⁵ and R ⁶ together comprise 2-8 non- hydrogen atoms. In some embodiments, the anion, X ^q~ , is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.

In some embodiments, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are identical, R ¹ and R ² are identical, and R ¹ and R ³ are different, R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl. In some embodiments, R ¹ and R ² together comprise 2-8 non- hydrogen atoms. In some embodiments, the anion, X ^q~ , is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are j ^' so-propyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl.

In some embodiments, R\ R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl.

In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl.

In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are hydrogen.

In some embodiments, wherein R ¹ , R ² , R ³ and R ⁴ are identical, R ⁵ and R ⁶ are identical, and R ¹ and R ⁵ are different, R ⁵ and R ⁶ together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, X ^q~ , is selected from Group 2 or 3.

In some embodiments, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are identical, R ¹ and R ² are identical, and R ¹ and R ³ are different, R ¹ and R ² together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, X ^q" , is selected from Group 2 or 3. In some embodiments, ^' wherein R ¹ , R ² , R ³ and R ⁴ are identical, R ⁵ and R ⁶ are identical, and R ¹ and R ⁵ are different, R ¹ and R ² together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, X ^q" , is selected from Group 2 or 3.

In some embodiments, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are identical, R ¹ and R ² are identical, and R ¹ and R ³ are different, R ³ and R ⁴ together comprise 2-8 non-hydrogen atoms. In some embodiments, the anion, X ^~ , is selected from Group 2 or 3.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are identical, R ⁵ and R ⁶ are different and R ¹ , R ⁵ and R ⁶ are different. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are identical and are C ₂ - ₂₀ alkyl, substituted Ci_ ₆ alkyl, or C ₂ -6 alkenyl, R ⁵ is H, Ci_ ₂ o alkyl, substituted Q.6 alkyl, or C _2- 6 alkenyl, R ⁶ is C ₂ - ₂₀ alkyl, substituted Ci_ ₆ alkyl, or C ₂ . ₆ alkenyl, and R ¹ , R ⁵ and R ⁶ are different.

In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical, R ¹ and R ² are different and R ¹ , R ² and R ³ are different. In some embodiments, R ³ , R ⁴ , R ⁵ and R ⁶ are identical and are C ₂ . ₂ o alkyl, substituted C _} . _e alkyl, or C ₂ -6 alkenyl, R ¹ and R ² are each independently H, Ci_ ₂ o alkyl, substituted C]_ ₆ alkyl, or C ₂ -6 alkenyl, and R ¹ , R ² and R ³ are different. In some embodiments, wherein R ¹ , R ² , R ³ and R ⁴ are identical, R ⁵ and R ⁶ are different and R ¹ , R ⁵ and R ⁶ are different, R ¹ , R ² , R ³ and R ⁴ are ethyl. In some embodiments, R ⁵ and R ⁶ together comprise 1 -6 non- hydrogen atoms. In some embodiments, the anion, X ^q~ , is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.

In some embodiments, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are identical, R ¹ and R ² are different and R ¹ , R ² and R ³ are different, R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl. In some embodiments, R ¹ and R ² together comprise 1-6 non- hydrogen atoms. In some embodiments, the anion, X ^q , is selected from Group 2 or 3. In some embodiments, the anion is selected from Group 3.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is hexyl.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1-carboxylethyl,

1 -carboxyl-2-hydroxypropyl, or l-carboxyl-2-methylpropyl. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-hydroxypropyl, or 1 -carboxyl-2-methylpropyl. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl. In some

embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is (S)- 1-carboxylethyl, (S)-l -carboxyl-2-hydroxypropyl, or (S)-l -carboxyl-2-methylpropyl. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is (S)-l -carboxyl-2-hydroxypropyl, or

(S)-l -carboxyl-2-methylpropyl. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is (S)-l -carboxylethyl. In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are -H and R ² , R ⁴ and R ⁶ are phenyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are wo-propyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are /so-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are -H,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-hydroxypropyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-methylpropyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are

2-carboxylpyrrolidinyl.

In some embodiments,

are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are -H and R ² , R ⁴ and R ⁶ are phenyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are iso-propyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl, R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are -H,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-hydroxypropyl, or R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-methylpropyl.

In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl. In some embodiments,

are 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl.

In some embodiments, one or more of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are chiral.

In some embodiments, one or more of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is (S)-l -carboxylethyl,

(S)- 1 -carboxyl-2-hydroxypropyl, or (S)- 1 -carboxyl-2-methylpropyl; or (S)- 1 -carboxyl-2-hydroxypropyl or (S)-l -carboxyl-2-methylpropyl; or (S)-l -carboxylethyl.

In some embodiments, R ¹ or R ² together comprise 3-7 non-hydrogen atoms, R ³ and R ⁴ together comprise 3-7 non-hydrogen atoms and R ⁵ or R ⁶ is chiral.

In some embodiments, R ¹ or R ² together comprise 3-7 non-hydrogen atoms, R ³ and R ⁴ together comprise 3-7 non-hydrogen atoms and R ⁵ or R ⁶ is (S)-l -carboxylethyl, (S)-l-carboxyl-2-hydroxypropyl, or

(S)-l -carboxyl-2-methylpropyl; or (S)-l-carboxyl-2-hydroxypropyl or (S)-l -carboxyl-2-methylpropyl; or (S)- 1 -carboxylethyl.

In some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is independently -NH-CH(R ^A )-C0 ₂ H, wherein R ^A is a side chain of a natural or non-natural alpha-amino acid.

Accordingly, in some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 ₂ H.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 ₂ H. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are ethyl, and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-(S)-2-C0 ₂ H.

In some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 ₂ H, -NH(CH(CH ₃ )C0 ₂ H),

-NH(CH(CH(OH)CH ₃ )C0 ₂ H), or -NH(CH(CH(CH ₃ ) ₂ )C0 ₂ H); or - H(CH(CH ₃ )C0 ₂ H),

-NH(CH(CH(OH)CH ₃ )C0 ₂ H), or -NH(CH(CH(CH ₃ ) ₂ )C0 ₂ H); or -pyrrolidinyl-2-C0 ₂ H,

-NH(CH(CH(OH)CH ₃ )C0 ₂ H) or -NH(CH(CH(CH ₃ ) ₂ )C0 ₂ H); or -NH(CH(CH(OH)CH ₃ )C0 ₂ H) or -NH(CH(CH(CH ₃ ) ₂ )C0 ₂ H); or -NH(CH(CH ₃ )C0 ₂ H).

In some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-(S)-2-C0 ₂ H, -NH((5)-CH(CH ₃ )C0 ₂ H),

-NH(CH((S)-CH(OH)CH ₃ )C0 ₂ H), or -NH((S)-CH(CH ₃ )C0 ₂ H); or -NH((S)-CH(CH ₃ )C0 ₂ H),

-NH(CH((S)-CH(OH)CH ₃ )C0 ₂ H) or -NH((S)-CH(CH(CH ₃ ) ₂ )C0 ₂ H); or -pyrrolidinyl-(S)-2-C0 ₂ H, -NH(CH((S)-CH(OH)CH ₃ )C0 ₂ H) or -NH((S)-CH(CH(CH ₃ ) ₂ )C0 ₂ H);

or -NH(CH((S)-CH(OH)CH ₃ )C0 ₂ H) or -NH((5)-CH(CH(CH ₃ ) ₂ )C0 ₂ H); or -NH((S)-CH(CH ₃ )C0 ₂ H).

In some embodiments, one or more of R ¹ - R ⁶ is independently -CH(R ^A )-C0 ₂ H, wherein R ^A is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group.

In some embodiments, one or more of R ¹ - R ⁶ is independently -CH(CH ₃ )C0 ₂ H,

-CH(CH(OH)CH ₃ )C0 ₂ H, or -CH(CH(CH ₃ ) ₂ )C0 ₂ H; or -CH(CH(OH)CH ₃ )C0 ₂ H

or - CH(CH(CH ₃ ) ₂ )C0 ₂ H; or -CH(CH ₃ )C0 ₂ H.

In some embodiments, one or more of R ¹ - R ⁶ is independently -(S)-CH(CH ₃ )C0 ₂ H,

-CH((S)-CH(OH)CH ₃ )C0 ₂ H, or -(S)-CH(CH(CH ₃ ) ₂ )C0 ₂ H; or -CH((5)-CH(OH)CH ₃ )C0 ₂ H

or -(S)-CH(CH(CH ₃ ) ₂ )C0 ₂ H; or -(S)-CH(CH ₃ )C0 ₂ H.

In some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are independently

-N(Ci_6 alkyl)-CH(R ^A )-C0 ₂ (Ci. ₆ alkyl), wherein R ^A is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group.

In some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are independently -N(Ci_6 alkyl)-CH(R ^A )-C0 ₂ H, wherein R ^A is a side chain of a natural or non-natural alpha-amino acid, provided that the side chain does not link to the alpha-amino group. In some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are independently -NH-CH(R ^A )-C0 ₂ (Ci_6 alkyl), wherein R ^A is a side chain of a natural or non-natural alpha-amino acid.

Accordingly, in some embodiments, one or more of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, is -pyrrolidinyl-2-C0 ₂ (Ci. ₆ alkyl). In some embodiments, R ¹ and R ² are identical, R ³ and R ⁴ are identical, and R ⁵ and R ⁶ are identical, and R ¹ , R ³ and R ⁵ are different.

In some embodiments, R ¹ and R ² are different, R ³ and R ⁴ are different, and R ⁵ and R ⁶ are different, R ¹ , R ³ and R ⁵ are identical, and R ² , R ⁴ and R ⁶ are different.

In some embodiments, R ¹ and R ² are different, R ³ and R ⁴ are different, and R ⁵ and R ⁶ are identical, R ¹ and R ³ are identical, R ¹ and R ⁵ are different, R ² and R ⁴ are identical, and R ² and R ⁶ are different. In some embodiments, wherein R ¹ and R ² are different, R ³ and R ⁴ are different, and R ⁵ and R ⁶ are identical, R ¹ and R ³ are identical, R ¹ and R ⁵ are different, R ² and R ⁴ are identical, and R ² and R ⁶ are different, R ¹ is butyl and R ² is methyl. In some embodiments, R ⁵ and R ⁶ together comprise 1 -6 non- hydrogen atoms.

In some embodiments, R ¹ and R ² are different, R ³ and R ⁴ are different, and R ⁵ and R ⁶ are different, R ¹ , R ³ and R ⁵ are identical, R ² and R ⁴ are identical, and R ² and R ⁶ are different.

In some embodiments, R ¹ and R ² are different, R ³ and R ⁴ are different, and R ⁵ and R ⁶ are different, R ¹ and R ³ are identical, R ¹ and R ⁵ are different, R ² and R ⁴ are identical, and R ² and R ⁶ are different.

In some embodiments, wherein R ¹ and R ² are different, R ³ and R ⁴ are different, and R ⁵ and R ⁶ are different, R ¹ and R ³ are identical, R ¹ and R ⁵ are different, R ² and R ⁴ are identical, and R ² and R ⁶ are different, R ¹ and R ² together comprise 3-7 non-hydrogen atoms. In some embodiments, R ¹ is butyl and R ² is methyl.

In some embodiments, R ¹ and R ² are different, R ³ and R ⁴ are different, R ⁵ and R ⁶ are different, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are different.

In some embodiments, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are identical and R ¹ and R ⁶ are different.

In some embodiments, R ¹ , R ² and R ³ are identical, R ³ and R ⁴ are different, and R ⁴ , R ⁵ and R ⁶ are identical.

In some embodiments, R ¹ , R ² and R ³ are identical, R ³ and R ⁴ are different, R ⁵ and R ⁶ are identical, and R ² , R ⁴ and R ⁶ are different.

In some embodiments, R ¹ and R ² are identical, R ³ and R ⁴ are identical, and R ¹ , R ³ , R ⁵ and R ⁶ are different.

In some embodiments, R ^D is (4-methylpiperazinyl)methyl, 2,3-difluoro-4-pyridyl, 3-fluoropyridyl, 5-methyl-2-furyl, [2-(trimethylsilyl)ethoxy]methyl, or bromomethyl.

In some embodiments, R ^F is perfluoro C ₁ . ₁ 2 alkyl.

In some embodiments, R ^F is perfluoro C ₂ _i2 alkenyl having one or more double bonds or perfluoro C ₂ -n alkynyl having one or more triple bonds.

In some embodiments, R ^F is selected from pentafluoroallyl, heptafluorobut-2-enyl, heptafluorobut-3-enyl, wo-heptafluorobutenyl, sec-heptafluorobutenyl, nonafluoropent-4-enyl, wo-nonafluoropentenyl, and -C ₆ Fi i . In some embodiments, R ^F is selected from fluoroethynyl, trifluoropropyn-l -yl, trifluoroprop-2-ynyl, pentafluorobut-2-ynyl, pentafluorobut-3-ynyl, heptafluoropent-3-ynyl, heptafluoropent-4-ynyl, and nonafluorohexynyl.

In some embodiments, R ^F is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, -C(CF ₃ ) ₃ , -CF ₂ N(CF ₃ )CF ₃ , -CF ₂ OCF ₃ , -CF ₂ S(0)CF ₃ ,

-CF ₂ S0 ₂ CF ₃ , -C ₂ F ₄ N(C ₂ F5)C ₂ F5, -CF=CF ₂ , -C(CF ₃ )=CFCF ₃ , -CF ₂ CF=CFCF ₃ ,

-CF=CFN(CF ₃ )CF ₃ , -CF ₂ S0 ₂ F, -C(CF ₃ )=CFCF ₃ , -CF ₂ CF=CFCF ₃ , and -CF=CFN(CF ₃ )CF ₃ .

In some embodiments, R ^F is trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.

In some embodiments, R ^F is perfluorophenyl optionally substituted by one or more perfluoro C,. ₆ alkyl. In some embodiments, R ^G is perfluoro C ₂ _i ₂ alkyl.

In some embodiments, R° is perfluoro C ₂ . _]2 alkenyl having one or more double bonds or perfluoro C ₂ _i ₂ alkynyl having one or more triple bonds.

In some embodiments, R ^G is selected from pentafluoroallyl, heptafluorobut-2-enyl, heptafluorobut-3-enyl, wo-heptafluorobutenyl, seoheptafluorobutenyl, nonafluoropent-4-enyl, wo-nonafluoropentenyl, and -C ₆ F _u .

In some embodiments, R ^G is selected from fluoroethynyl, trifluoroprop-l-ynyl, trifluoroprop-2-ynyl, pentafluorobut-2-ynyl, pentafluorobut-3-ynyl, heptafluoropent-3-ynyl, heptafluoropent-4-ynyl, and nonafluorohexynyl.

In some embodiments, R ^G is selected from pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, — C(CF ₃ ) ₃ , -CF ₂ N(CF ₃ )CF ₃ , -CF ₂ OCF ₃ , -CF ₂ S(0)CF ₃ , -CF ₂ S0 ₂ CF ₃ ,

-C ₂ F ₄ N(C ₂ F ₅ )C ₂ F5, -CF=CF ₂ , -C(CF ₃ )=CFCF ₃ , -CF ₂ CF=CFCF ₃ , -CF=CFN(CF ₃ )CF ₃ ,

-CF ₂ S0 ₂ F, -C(CF ₃ )=CFCF ₃ , -CF ₂ CF=CFCF ₃ or -CF=CFN(CF ₃ )CF ₃ .

In some embodiments, R ^G is pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.

In some embodiments, R ^G is perfluorophenyl optionally substituted by one or more perfluoro Ci_ ₆ alkyl. In some embodiments, wherein two or more R ^F or two or more R ^G are present in the anion, X ^q~ , any two or more R ^F or any two or more R ^G may be connected by a single or a double bond to form a cyclic, bicyclic or polycyclic anion.

In some embodiments, R ^J is phenyl substituted with methyl, ethyl, propyl, «ο-propyl, tert-butyl, nitro, fluoro, chloro, bromo, iodo, hydroxyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,

trifluoromethylsulfonyl, -NH ₂ , or -N(CH ₃ ) ₂ . In some embodiments, R ^J is phenyl disubstituted with methyl, fluoro, chloro, bromo, hydroxyl, or methoxy.

In some embodiments, R ^J is 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl, or 2,4,5-trimethylphenyl.

In some embodiments, R is perfluorophenyl. In some embodiments, R ^J is heteroaryl or heterocyclyl optionally substituted by one or more R ^K , wherein the heteroaryl or heterocyclyl is acridinyl, benz-2, 1 ,3 -oxadiazolyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzofuryl, benzopyrazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, carbazolyl, cinnolinyl, furyl, imidazolyl, IH-indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolyl, quinazolinyl, quinolinyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, 2H-thiopyranyl, 4H-thiopyranyl, or triazolyl.

In some embodiments, the anion, X ^q~ is selected from [(CF ₃ S0 ₂ ) ₂ N] ^" , [(CF ₃ S0 ₂ )NC(0)CF ₃ ] ^" ,

[(FS0 ₂ ) ₂ N]- [CF ₃ CF ₂ S0 ₃ ] ^" , [(C ₂ F ₅ S0 ₂ ) ₂ N] ^" , [(C ₂ F ₅ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C] ^" , [CF ₃ CF ₂ C(0)C>r,

[P(C ₂ F ₅ ) ₃ F ₃ ]-, [P(CF ₃ ) ₃ F ₃ ]-, [P(C ₂ F ₄ H)(CF ₃ ) ₂ F ₃ ] , [P(C ₂ F ₃ H ₂ ) ₃ F ₃ ] , [P(C ₂ F ₅ )(CF ₃ ) ₂ F ₃ ] ^~ , [P(C ₆ F ₅ ) ₃ F ₃ ] , [P(C ₃ F ₇ ) ₃ F ₃ ]-, [P(C ₄ F ₉ ) ₃ F ₃ ]-, [P(C ₂ F ₅ ) ₂ F ₄ ]-, [(C ₂ F ₅ ) ₂ P(0)Or, [(C ₂ F ₅ )P(0)0 ₂ ] ² - [P(C ₆ F ₅ ) ₂ F ₄ ]- [(CF ₃ ) ₂ P(0)Or, [(C ₄ F ₉ ) ₂ P(0)0]-, [CF ₃ P(0)0 ₂ ] ² [BF ₃ (CF ₃ )] ^' , [BF ₂ (C ₂ F ₅ ) ₂ r, [BF ₃ (C ₂ F ₅ )F, [BF ₂ (CF ₃ ) ₂ ] ^" , [B(C ₂ F ₅ ) ₄ ] ^" , [BF ₃ (CN)] ^{^} , [BF ₂ (CN) ₂ r, [B(CN) ^~ , [B(CF ₃ ) ₄ ] ^" , [N(CF ₃ ) ₂ ] ^" , [N(CN ₂ ) ₂ ] ^" ,

In some embodiments, the anion, X ^q , is selected from [P(C _n F ₂ n ₊ i- _m H _m ) _y F ₆ -y] , [BF _Z R ^F ₄ _ _Z ] a d

[BF ₂ (CN) ₄ - _Z ] ^~ , wherein n is 1 to 20; m is 0, 1, 2, or 3; y is 1, 2, 3, or 4; and z is 0, 1, 2, or 3.

In some embodiments, n is 1 to 12.

In some embodiments, the anion, X ^q~ is [B(CN) ₄ ] ^~ , [(C ₂ F ₅ ) ₃ PF ₃ ] ^" , [(C ₂ F ₅ )2PF ₄ ] ^" , [(C ₄ F ₉ ) ₃ PF ₃ ] ^~

[(C ₃ F ₇ ) ₃ PF ₃ ] ^" , [B(C ₂ F ₅ )F ₃ ] ^" , or [B(CF ₃ ) ₄ ] ^" . In some embodiments, the anion is [B(CN) ₄ ] ^" , [(C ₂ F ₅ ) ₃ PF ₃ ] ^" , or [B(C ₂ F ₅ )F ₃ ] . In some embodiments, the anion, X ^q~ is a group 1 anion selected from F ^~ , Br ^~ , Γ, [HF ₂ ] ^" , [SCN] ^~ ,

[NCO]- [ΝΟ3Γ, [AlC r, [A1 ₂ C1 ₇ ]-, [PF ₆ ]-, and [SnCl ₃ ]-

In some embodiments, the anion, X ^q~ , is the group 1 anion [SnCl ₃ ] ^~ .

In some embodiments, the anion, X ^q~ , is a group 1 anion selected from F-, Br ^~ , Γ, [HF ₂ ]-, [SCN] ^~ ,

[NCO] ^" [NO ₃ ]- [A1C1 ₄ ]- [A1 ₂ C1 ₇ ]-, and [PF ₆ ] ^" . In some embodiments, the anion, X ^q_ , is a group 2 anion selected from [SeCN]-, [CF ₃ SO ₃ ]-, [FHOMe]-, [FHOEtr, [FHOPr]-, [MeOS0 ₃ ] ^~ [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0]-, [CH ₃ C ₆ H ₄ S0 ₃ ] ^" ,

((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4- trifluoroborate, 5-methylfuran-2-trifluoroborate, [2-(trimethylsilyl)ethoxy]methyltrifluoroborate, and [BrCH ₂ BF ₃ ] ^" .

In some embodiments, the anion, X ^q" , is a group 2 anion selected from [SeCN] ^" , [CF ₃ S0 ₃ ] ^" , [FHOMe] ^" , [FHOEt] ^" [FHOPr] ^" [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" , and [CH ₃ C ₆ H ₄ S0 ₃ ] ^" . In some embodiments, the anion, X ^q" , is a group 3 anion selected from [(CF ₃ S0 ₂ )2N] ^~ ,

[(CF ₃ S0 ₂ )NC(0)CF ₃ r, [(FS0 ₂ ) ₂ N]-, [CF ₃ CF ₂ S0 ₃ ] ^" [C^SO,] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0]-, [(C ₂ F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)0] ^" , [(C ₂ F ₅ 0) ₂ P(0)0] ^" [BF ₃ (CF ₃ ) ₃ ] ^" [BF ₃ (C ₂ F ₅ ) ₃ ] ^" [BF ₃ (CN)] ^" , [B(CN) ₄ ] ^" , [N(CN) ₂ ] ^" and [C(CN) ₃ ] ^" .

In some embodiments, the anion, X ^q" , is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^~ , [SCN] ^" , [NCO] ^" , [N0 ₃ ] ^" , [A1C1 ₄ ]-, [A1 ₂ C1 ₇ ]- [PF ₆ ]-, [SnCl ₃ ] ^" ,

[SeCN] ^" , [CF ₃ S0 ₃ ] ^" , [FHOMe] ^" , [FHOEt] ^" , [FHOPr] , [MeOS0 ₃ ] ^" [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^"

[CH ₃ C ₆ H ₄ S0 ₃ ] ^" , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate,

3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^~ ,

[(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ]-, [C ₄ F ₉ S0 ₃ ]-, [(CF ₃ CF ₂ S0 ₂ ) ₂ N)]-,

[(CF ₃ S0 ₂ ) ₃ C] - [(FS0 ₂ ) ₃ C] - [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0] ^" , [(C ₂ F ₅ ) ₂ P(0)0] ^" , [(CF ₃ 0) ₂ P(0)0] ,

[(C ₂ F ₅ 0) ₂ P(0)0]- [BF ₃ (CF ₃ ) ₃ ]- [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" [B(CN) ₄ ] ^" , [N(CN) ₂ ] ^" , and [C(CN) ₃ ] ^" .

In some embodiments, the anion, X ^q~ , is selected from F ^" , Br ^~ , Γ, [HF ₂ ] ^~ [SCN] ^" , [NCO] ^~ , [N0 ₃ ] ^~ , [A1C1 ₄ ] ^" , [A1 ₂ C1 ₇ ]-, [PF ₆ ]-,

[SeCN] ^" , [CF ₃ S0 ₃ ] ^" , [FHOMe] ^' , [FHOEt] ^" [FHOPr] ^" [MeOS0 ₃ ] ^" [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^"

[CH ₃ C ₆ H ₄ S0 ₃ ] ^" , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^" , [(CF ₃ S0 ₂ )NC(0)CF ₃ ] ^" , [(FS0 ₂ ) ₂ N] ^" [CF ₃ CF ₂ S0 ₃ ] ^" [C ₄ F ₉ S0 ₃ ] ^" [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" [(CF ₃ S0 ₂ ) ₃ Cr, [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ ) ₃ F ₃ ] ^" [(CF ₃ ) ₂ P(0)0] ^" , [(C ₂ F ₅ ) ₂ P(0)0] ^" [(CF ₃ 0) ₂ P(0)0]-,

[(C ₂ F ₅ 0) ₂ P(0)0] ^" , [BF ₃ (CF ₃ ) ₃ ] , [BF ₃ (C ₂ F ₅ ) ₃ ] ^" [BF ₃ (CN)] ^" , [B(CN) ₄ ] ^" , [N(CN) ₂ r, and [C(CN) ₃ ]-.

In some embodiments, the anion, X ^q" , is selected from F ^~ , Br ^" , Γ, [HF ₂ ] ^" , [SCN] ^" , [NCO] ^" , [N0 ₃ ] ^" , [A1C1 ₄ ]-, [A1 ₂ C1 ₇ ]-, [PF ₆ ] ^" , [SnCl ₃ ] ^"

[SeCN] ^" , [CF ₃ S0 ₃ ] ^~ , [FHOMe] ^" , [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" ,

[(CF ₃ S0 ₂ ) ₂ N]- [(CF ₃ S0 ₂ )NC(0)CF ₃ r, [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ] ^" , [C^SO,] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" [(CF ₃ S0 ₂ ) ₃ C] ^" [(FS0 ₂ ) ₃ C] ^" , [P(C ₂ F ₅ ) ₃ F ₃ ] ^" , [(CF ₃ ) ₂ P(0)0] ^" , [(C ₂ F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)0] ^~

[(C ₂ F ₅ 0) ₂ P(0)0] ^" , [BF ₃ (CF ₃ ) ₃ ] ^" , [BF ₃ (C ₂ F ₅ ) ₃ ] ^" [BF ₃ (CN)] ^" [B(CN) ₄ ] ^" , [N(CN) ₂ ] ^" , and [C(CN) ₃ ] ^" . In some embodiments, the anion, X ^q" , is selected from F ^~ , Br-, Γ, [HF ₂ ] ^~ , [SCN]-, [NCO] ^" , [N0 ₃ ]- [AICI4]- [A1 ₂ C1 ₇ ]-, [PF ₆ ]-

[SeCN]-, [CF ₃ SO ₃ ] ^" , [FHOMe]-, [FHOEt] ^" , [FHOPr]- [MeOS0 ₃ ]-, [EtOS0 ₃ ]-, [(BuO) ₂ P(0)0] ^' ,

[CF^C^SO,]-,

[(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ r, [(FS0 ₂ ) ₂ N]-, [CF ₃ CF ₂ S0 ₃ ]-, [C^SO,]-, [(CF ₃ CF ₂ S0 ₂ ) ₂ N)]-, [(CF ₃ S0 ₂ ) ₃ Cr, [(FS0 ₂ ) ₃ C]- [P(C ₂ F ₅ ) ₃ F3]-, [(CF ₃ ) ₂ P(0)0]-, [(C ₂ F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)0]- [(C ₂ F ₅ 0) ₂ P(0)0]- [BF ₃ (CF ₃ ) ₃ ]-, [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)]-, [B(CN) ₄ ]- [N(CN) ₂ ] , and [C(CN) ₃ ]-

In some embodiments, the anion, X ^q~ , is [NH ₂ -CH(R ^A )C(0)0] ^" .

Accordingly, in some embodiments, the anion, X ^q~ , is [pyrrolidinyl-2-COO] ^~ . In some embodiments, the anion, X ^q" , is selected from F-, Br- Γ, [N0 ₃ ] ^" , [PF ₆ ]- [SnCl ₃ ] ^~ [SCN] ^" , [NCO] , [CF ₃ S0 ₃ r, [CH3OSO3]-, [CJHSOSOJ]- [C ₆ F ₅ S0 ₃ ]-, [(BuO) ₂ P(0)0]- [CH ₃ C ₆ H ₄ S03] ^" ,

[(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" [P(C ₂ F ₅ ) ₃ F ₃ ]- [B(CN) ₄ ]- and [N(CN) ₂ ] ^" .

In some embodiments, the anion, X ^q" , is selected from F ^~ , Br-, Γ, [N0 ₃ ]- [SnCl ₃ ]-, [SCN]-, [NCO]-, [CF ₃ SO3]- [CH ₃ OSO ₃ ]-, [(BuO) ₂ P(0)0]-, [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [P(C ₂ F ₅ )3F ₃ ]-, [B(CN) ₄ ]-, and [N(CN) ₂ ]-.

In some embodiments, the anion, X ^q- , is selected from F-, Β , [N0 ₃ ]-, [PF ₆ ]-, [SCN]- [CF ₃ S0 ₃ ]-,

[CH ₃ OSO ₃ ]-, [C ₂ H ₅ OS0 ₃ ]- [C ₆ F ₅ S0 ₃ ]-, [CH3C6H S03]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ]-.

In some embodiments, the anion, X ^q- is selected from Br ^" , Γ, [N0 ₃ ]- [PF ₆ ]-, [SnCl ₃ ]-, [SCN]-, [NCO]- [CF3SO ₃ ]- [CH3OSO3]- [C ₂ H ₅ OS0 ₃ ]- [C ₆ F ₅ S0 ₃ r, [(BuO) ₂ P(0)0]- [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ r, [(C ₂ F ₅ S0 ₂ ) ₂ N)]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [B(CN) ₄ ]-, and [N(CN) ₂ ]-.

In some embodiments, the anion, X ^q- , is selected from Br-, [N0 ₃ ]-, [PF ₆ ]-, [SCN]-, [CF ₃ SO ₃ ]-,

[CH3OSO3]-, [C ₂ H ₅ OS0 ₃ ]- [C ₆ F ₅ S0 ₃ ]-, [CH ₃ C ₆ H ₄ S0 ₃ ] ^" , [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]- [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ]-. In some embodiments, the anion, X ^q- is selected from [N0 ₃ ]- [PF ₆ ]- [SnCl ₃ ]-, [SCN]-, [NCO]-,

[CF ₃ S0 ₃ r, [CH ₃ OS0 ₃ ]-, [C ₂ H ₅ OS0 ₃ ]-, [C ₆ F ₅ S0 ₃ ]- [(BuO) ₂ P(0)0]-, [CH _J C^SO _J ]-, [(CF ₃ S0 ₂ ) ₂ N]- [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [B(CN) ₄ ]-, and [N(CN) ₂ ]-.

In some embodiments, the anion, X ^q- , is selected from [N0 ₃ ]-, [PF ₆ ]-, [SCN] , [CF ₃ S0 ₃ ]-, [CH ₃ OS0 ₃ ]-, [C ₂ H ₅ OS0 ₃ ]-, [C ₆ F ₅ S0 ₃ ]- [CH _J C^SO _J F, [(CF ₃ S0 ₂ ) ₂ N]- [(FS0 ₂ ) ₂ N]- [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ]-. In some embodiments, the anion, X ^q~ is selected from [PF ₆ ] ^~ , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ] ^" , [CeFsSO,]-, [CH^^SO,] ^" , [(CF ₃ S0 ₂ ) ₂ N] ^" , [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" and [N(CN) ₂ ] ^"

In some embodiments, the anion, X ^q" , is F ^~ .

The invention also contemplates embodiments in which the cation, Y^, is as identified in any of the embodiments disclosed above and the anion, X ^" , is as identified in any of the embodiments disclosed above.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, C ₂ o alkyl, substituted Ci_2o alkyl, C ₂ . ₂ o alkenyl, substituted C ₂ . ₂₀ alkenyl, aryl, and substituted aryl; and

R ⁴ and R ⁶ are each independently selected from C _-2 o alkyl, substituted Ci. ₂ o alkyl, C ₂ . ₂ o alkenyl, substituted C ₂ . ₂₀ alkenyl, aryl, and substituted aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and

the anion, X ^q" is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^" , [SCN] ^" , [NCO] ^" , [N0 ₃ ] ^~ , [AICL,] ^" [A1 ₂ C1 ₇ ] ^~ [PF ₆ ] ^" , [SnCl ₃ ]- [SeCN]-, [CF ₃ S0 ₃ ] ^" , [FHOMef, [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" ,

[CH ₃ C ₆ H ₄ S0 ₃ ] , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifIuoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^" , [(CF ₃ S0 ₂ )NC(0)CF ₃ r, [(FS0 ₂ ) ₂ N] ^~ [CF ₃ CF ₂ S0 ₃ ] ^" , [C4F9SO3]- [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ ) ₃ F ₃ ] ^" , [(CF ₃ ) ₂ P(0)0]- [(C ₂ F ₅ ) ₂ P(0)0] ^" [(CF ₃ 0) ₂ P(0)0]-

[(C ₂ F ₅ 0) ₂ P(0)0]-, [BF ₃ (CF ₃ ) ₃ ] ^{^} , [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" [B(CN) ₄ ]-, [ (C ) ₂ ]-, and [C(CN) ₃ ] .

In some embodiments, R ¹ , R ² and R ³ are each independently selected from -H, Ci. ₂ o alkyl, substituted Ci_ ₂₀ alkyl, C ₂ . ₂ o alkenyl, substituted C ₂ . ₂ o alkenyl, aryl, and substituted aryl; and

R ⁴ is selected from C ₂ - ₂ o alkyl, substituted Ci-20 alkyl, C ₂ . ₂₀ alkenyl, substituted C ₂ . ₂₀ alkenyl, aryl, and substituted aryl; and

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and

the anion, X ^q" , is selected from F ^" , Br ^" , Γ, [HF,] ^" [SCN] ^" , [NCO] ^" , [NO ₃ ] ^" , [AICI ₄ ] ^" , [AI2CI7] ^" , [PF ₆ ] ^" [SnCl ₃ ] ^" ,

[SeCN] ^' [CF ₃ S0 ₃ ]-, [FHOMe] ^" , [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" ,

[CH ₃ C ₆ H ₄ S0 ₃ ] ^" , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^" , [(CF ₃ S0 ₂ )NC(0)CF ₃ ] ^" , [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ] ^" , [C ₄ F ₉ S0 ₃ ] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" , [(CF ₃ S0 ₂ ) ₃ C] ^" [(FS0 ₂ ) ₃ C]- [P(C ₂ F ₅ ) ₃ F ₃ ] ^" , [(CF ₃ ) ₂ P(0)0] ^" , [(C ₂ F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)0] ^"

[(C ₂ F ₅ 0) ₂ P(0)0]-, [BF ₃ (CF ₃ ) ₃ ]-, [BF ₃ (C ₂ F ₅ ) ₃ ] ^" , [BF ₃ (CN)r, [B(CN) ₄ ]-, [ (CN) ₂ ]-, and [C(CN) ₃ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci.20 alkyl, C ₂ _ ₂₀ alkenyl, and aryl;

R ⁴ and R ⁶ are each independently selected from C _2-2 o alkyl, substituted Ci_ ₂ o alkyl, C2-20 alkenyl, and aryl; and

the anion, X ^q" , is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^" , [SCN] ^" , [NCO] ^" , [N0 ₃ ] ^' , [AICU] ^"" , [A1 ₂ C1 ₇ ] ^~ , [PF ₆ ] ^" ,

[Sncy-,

[SeCN] ^" , [CF ₃ S0 ₃ ] ^" , [FHOMe] ^" , [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ]-, [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" ,

[CH ₃ C ₆ H ₄ S0 ₃ ] ^~ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^~ ,

[(CF ₃ S0 ₂ ) ₂ N]- [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ] ^" [C ₄ F ₉ S0 ₃ ] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" , [(CF ₃ S0 ₂ ) ₃ C]- [(FS0 ₂ ) ₃ C]- [P(C ₂ F ₅ ) ₃ F ₃ ]- [(CF ₃ ) ₂ P(0)0] ^" [(C ₂ F ₅ ) ₂ P(0)0] ^" , [(CF ₃ 0) ₂ P(0)0] ^" ,

[(C ₂ F ₅ 0) ₂ P(0)0]-, [BF ₃ (CF ₃ ) ₃ ]- [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" , [B(CN) ₄ ] ^~ , [N(CN) ₂ ] ^" , and [C(CN) ₃ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci. ₂₀ alkyl, and C2-20 alkenyl;

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂₀ alkyl, substituted C]. ₂ o alkyl, and C ₂ . ₂ o alkenyl; and the anion, X ^q" is selected from F , Br ^" , Γ, [HF ₂ ] ^~ , [SCN] , [NCO] ^" [N0 ₃ ] [AICU] ^" , [A1 ₂ C1 ₇ ] ^" , [PF ₆ ] ^" , [SeCN] ^" , [CF ₃ S0 ₃ ] ^" [FHOMe]-, [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" ,

[CH ₃ C ₆ H ₄ S0 ₃ ] ^~ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^" , [(CF ₃ S0 ₂ )NC(0)CF ₃ ] ^" , [(FS0 ₂ ) ₂ N] ^" [CF ₃ CF ₂ S0 ₃ ] ^" , [C ₄ F ₉ S0 ₃ ] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" , [(CF ₃ S0 ₂ ) ₃ Cr, [(FS0 ₂ ) ₃ C] ^" , [P(C ₂ F5) ₃ F ₃ ] ^" , [(CF ₃ ) ₂ P(0)0] ^" , [(C2F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)Or,

[(C ₂ F ₅ 0) ₂ P(0)0]-, [BF ₃ (CF ₃ ) ₃ ]-, [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" [B(CN) ₄ ] ^" , [N(CN) ₂ ]-, and [C(C ) ₃ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted C1.6 alkyl, C ₂ . ₆ alkenyl, and aryl;

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, substituted Ci_ ₆ alkyl, C ₂ _6 alkenyl, and aryl; and

the anion, X ^q" , is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^" , [SCN]-, [NCO] ^" [N0 ₃ ] ^" [AICU] ^" , [A1 ₂ C1 ₇ ] ^" , [PF ₆ ] ^" , [SnCl ₃ ] ^" ,

[SeCN] ^" , [CF ₃ S0 ₃ ]- [FHOMe] ^" , [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" ,

[CH ₃ CeH ₄ S0 ₃ ] ^" , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate, [2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^~ ,

[(CF ₃ S0 ₂ ) ₂ N] ^" , [(CF ₃ S0 ₂ )NC(0)CF ₃ r, [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ r, [C ₄ F ₉ S0 ₃ ]-, [(CF ₃ CF ₂ S0 ₂ ) ₂ N)]-, [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0] ^" [(C ₂ F ₅ ) ₂ P(0)0]- [(CF ₃ 0) ₂ P(0)0]- [(C ₂ F ₅ 0) ₂ P(0)0]- [BF ₃ (CF ₃ ) ₃ ]-, [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" , [B(CN) ₄ ] ^" , [N(CN) ₂ ] ^" , and [C(CN) ₃ ] ^" In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci- ₂ o alkyl, substituted Ci_6 alkyl, and C ₂ .<, alkenyl;

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂₀ alkyl, substituted Ci_ ₆ alkyl, and C ₂ . ₆ alkenyl; and the anion, X ^q_ , is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^" , [SCN] ^" , [NCO]-, [N0 ₃ T, [A1C ] ^~ [A1 ₂ C1 ₇ ]-, [PF ₆ ] ^~ , [SeCN]-, [CF ₃ S0 ₃ r, [FHOMe] ^" , [FHOEt] ^" , [FHOPrf, [MeOS0 ₃ ] ^" [EtOS0 ₃ ] ^~ [(BuO) ₂ P(0)0]

[CH ₃ C ₆ H ₄ S0 ₃ ] ^~ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ,

[(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ ]- [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ] ^" , [C^SO,] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" , [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]- [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0] ^" , [(C ₂ F _S ) ₂ P(0)0]- [(CF ₃ 0) ₂ P(0)0] ^" ,

[(C ₂ F ₅ 0) ₂ P(0)0]-, [BF ₃ (CF ₃ ) ₃ ]- [BF ₃ (C ₂ F ₅ ) ₃ ] ^~ , [BF ₃ (CN)] ^" [B(CN) ₄ ]-, [N(CN) ₂ ] ^" , and [C(CN) ₃ ] ^"

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, hydroxy Ci- alkyl, carboxyl Q-6 alkyl, Ci_6 alkoxycarbonyl C|.6 alkyl, C .e alkoxy C e alkyl, Q-e alkyl-NH ₂ , Ci _-6 alkylamino Ci_ ₆ alkyl, carboxyl hydroxy Ci-6 alkyl, C ₂ -e alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C _2-20 alkyl, hydroxy Ci_ ₆ alkyl, carboxyl C]_ ₆ alkyl, Ci_6 alkoxycarbonyl Cue alkyl, Ci_6 alkoxy Ci.e alkyl, d_ ₆ alkyl-NH ₂ , C[. ₆ alkylamino ue alkyl, carboxyl hydroxy C e alkyl, C ₂ -e alkenyl, and aryl; and

the anion, X ^q~ is selected from F ^" , ΒΓ, Γ, [HF ₂ ] ^" , [SCN]-, [NCO] ^" [N0 ₃ ] ^_ , [AICL,]-, [A1 ₂ C1 ₇ ] ^~ [PF ₆ ] ^" [SnCl ₃ ]-,

[SeCN] ^" , [CF ₃ S0 ₃ ]-, [FHOMe] ^" [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" ,

[CH ₃ CeH ₄ S0 ₃ ] , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy] methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^" , [(CF ₃ S0 ₂ )NC(0)CF ₃ ] ^" , [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ] ^" , [C ₄ F ₉ S0 ₃ ] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" , [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]- [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0]-, [(C ₂ F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)0] ^"

[(C ₂ F ₅ 0) ₂ P(0)0] , [BF ₃ (CF ₃ ) ₃ ]-, [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" , [B(CN) ₄ ] ^" , [N(CN) ₂ ] ^" , and [C(CN) ₃ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, hydroxy Cj.6 alkyl, carboxyl Ci.e alkyl, Ci_ ₆ alkoxycarbonyl Ci _-6 alkyl, Cue alkoxy Cj. ₆ alkyl, C]. ₆ alkyl-NH ₂ , C _]-6 alkylamino C,. ₆ alkyl and C _2-6 alkenyl; and R ⁴ and R ⁶ are each independently selected from C ₂ - ₂ 0 alkyl, hydroxy Ci_ ₆ alkyl, carboxyl Ci_6 alkyl, Ci _-6 alkoxycarbonyl Ci _-6 alkyl, Ci _-6 alkoxy Ci _-6 alkyl, Ci„ ₆ alkyl-NH ₂ , C,. ₆ alkylamino Ci _-6 alkyl and C ₂ . ₆ alkenyl; and

the anion, X ^q_ , is selected from F, Br ^" , Γ, [HF ₂ ] ^~ , [SCN] ^~ , [NCO]-, [N0 ₃ ] ^" , [AICI ₄ ] ^" , [A1 ₂ C1 ₇ ] ^" . [PF ₆ r, [SeCN]- [CF3SO3]- [FHOMe] ^" , [FHOEt]-, [FHOPr] , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^' ,

[CH3C6H SO3] ^" , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N]- [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ]- [C^SOa] ^" [(CF ₃ CF ₂ S0 ₂ ) ₂ N)]-, [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0] , [(C ₂ F ₅ ) ₂ P(0)0] -, [(CF ₃ 0) ₂ P(0)0]-,

[(C ₂ F ₅ 0) ₂ P(0)0]-, [BF ₃ (CF ₃ ) ₃ ]- [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" , [B(CN) ₄ ]-, [N(CN) ₂ ]- and [C(CN) ₃ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci- ₂₀ alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, carboxyl hydroxy Ci. ₆ alkyl, C _2-6 alkenyl, and aryl; and

R ⁴ and R ⁶ are each independently selected from C _2-2 o alkyl, hydroxy Ci_ ₆ alkyl, carboxyl Ci _-6 alkyl, carboxyl hydroxy C _1-6 alkyl, C _2- 6 alkenyl, and aryl; and

the anion, X ^q_ , is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^" , [SCN] ^" , [NCO] ^" , [Ν0 ₃ Γ, [AIC ] ^" , [A1 ₂ C1 ₇ ]-, [PF ₆ ] ^" , [SnCl ₃ ]-

[SeCN]- [CF3SO ₃ ] ^" , [FHOMe] ^" [FHOEt]-, [FHOPr] ^" [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0]- [CH ₃ C ₆ H ₄ SO ₃ ]-, ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^~ ,

[(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ] ^" , [C ₄ F ₉ S0 ₃ ]- [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" [(CF ₃ S0 ₂ ) ₃ C]- [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ )3F ₃ ]-, [(CF ₃ ) ₂ P(0)0] ^" [(C ₂ F ₅ ) ₂ P(0)0] , [(CF ₃ 0) ₂ P(0)0] ^"

[(C ₂ F ₅ 0) ₂ P(0)0]- [BF ₃ (CF ₃ ) ₃ ]- [BF ₃ (C ₂ F ₅ ) ₃ ] ^" , [BF ₃ (CN)r, [B(CN) ₄ ] ^" [N(CN) ₂ ]-, and [C(CN) ₃ ] ^" . In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci. ₂ o alkyl, hydroxy Ci-6 alkyl, carboxyl Ci_6 alkyl, and C ₂ . ₆ alkenyl;

R ⁴ and R ⁶ are each independently selected from C _2-20 alkyl, hydroxy Ci _-6 alkyl, carboxyl Ci_ ₆ alkyl, and C2-6 alkenyl; and

the anion, X ^q~ , is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^~ [SCN] ^" [NCO] ^" , [N0 ₃ ] ^_ , [AICI ₄ ] ^" , [Al ₂ Cl ₇ r, [PF ₆ ] ^" [SeCN] [CF3SO3] , [FHOMe] [FHOEt] [FHOPr] ^" , [MeOSO,] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ,

[CH ₃ C ₆ H ₄ S0 ₃ ] ^" , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^~ ,

[(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ ]- [(FS0 ₂ ) ₂ N] ^~ [CF ₃ CF ₂ S0 ₃ r, [C^SO,] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)]- [(CF ₃ S0 ₂ ) ₃ C]- [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0]- [(C ₂ F ₅ ) ₂ P(0)0]- [(CF ₃ 0) ₂ P(0)Or,

[(C ₂ F ₅ 0) ₂ P(0)0]- [BF ₃ (CF ₃ ) ₃ ]- [BF ₃ (C ₂ F ₅ ) ₃ ]- [BF ₃ (CN)] ^" , [B(CN) ₄ ] ^" [N(CN) ₂ r, and [C(CN) ₃ ]- In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, hydroxy C]-6 alkyl, and C2-6 alkenyl;

R ⁴ and R ⁶ are each independently selected from C2-20 alkyl, hydroxy Ci_ ₆ alkyl, carboxyl C _]-6 alkyl, and C ₂ -6 alkenyl; and

the anion, X ^q" , is selected from F ^~ , Br , Γ, [HF ₂ ] ^~ [SCN] ^" , [NCO] ^" [N0 ₃ ] ^~~ , [AICU] ^" , [A1 ₂ C1 ₇ ] ^" , [PF ₆ ] ^" , [SeCN] ^" , [CF3SO3] ^" , [FHOMe] ^" , [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^~ , [(BuO) ₂ P(0)0] ^" ,

[CH ₃ C ₆ H ₄ S0 ₃ ] ^~ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] - [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N] ^" [CF ₃ CF ₂ S0 ₃ ] , [C ₄ F ₉ S0 ₃ ]-, [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^~ [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ Cr, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [(CF ₃ ) ₂ P(0)0]-, [(C ₂ F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)0] ^"

[(C ₂ F ₅ 0)2P(0)0]- [BF ₃ (CF ₃ ) ₃ ] ^" [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^~ , [B(CN) ₄ ]-, [N(CN) ₂ ] ^" and [C(CN) ₃ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, substituted Ci-20 alkyl, C ₂ . ₂₀ alkenyl, and aryl;

R ⁴ and R ⁶ are each independently selected from C ₂ - ₂ o alkyl, substituted Ci. ₂ o alkyl, C ₂ . ₂ o alkenyl, and aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and

the anion, X ^q" , is selected from IT, Br ^" , Γ, [N0 ₃ ] ^" [PF ₆ ] ^" , [SnCl ₃ ] ^" , [SCN] ^' , [NCO] ^" , [CF ₃ S0 ₃ ] ^"

[CH ₃ OS0 ₃ ]-, [C ₂ H ₅ OS0 ₃ ]-, [C ₆ F ₅ S0 ₃ r, [(BuO) ₂ P(0)0] , [CI^C^SO,] ^" , [(CF ₃ S0 ₂ ) ₂ N] [(FS0 ₂ ) ₂ N] ^~ [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [B(CN) ₄ ] ^" and [N(CN) ₂ ]-.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci_ ₂₀ alkyl, C ₂ . ₂₀ alkenyl, and aryl;

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂ o alkyl, substituted Ci _-2 o alkyl, C _2-20 alkenyl, and aryl; and

the anion, X ^q" is selected from F ^" , Br ^" , Γ, [N0 ₃ ] ^_ , [PF ₆ ] ^" , [SnCl ₃ ] ^" , [SCN] ^" , [NCO] ^" , [CF ₃ S0 ₃ ] ^" ,

[CH ₃ OS0 ₃ ]-, [C ₂ H ₅ OS0 ₃ ] ^" , [CeFjSO,] ^" [(BuO) ₂ P(0)0] ^" [CH.C^SO,] ^" [(CF ₃ S0 ₂ ) ₂ N] , [(FS0 ₂ ) ₂ N] ^" [C ₂ F ₅ S0 ₃ ] ^" , [(C ₂ F ₅ S0 ₂ ) ₂ N)]-, [P(C ₂ F ₅ ) ₃ F ₃ ] ^" , [B(CN) ₄ ] ^" , and [N(CN) ₂ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, substituted Ci. ₂₀ alkyl, C _2-20 alkenyl, and aryl;

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂ o alkyl, substituted Ci_ ₂ o alkyl, C ₂ _2o alkenyl, and aryl; or

R ⁵ and R ⁶ form, together with the nitrogen atom to which they are attached, a heterocyclyl or substituted heterocyclyl; and the anion, X ^q_ , is selected from Br ^" , Γ, [Ν0 ₃ ] ^~ , [PF ₆ ] ^" [SnCl ₃ ] ^~ , [SCN] ^" , [NCOf, [CF ₃ S0 ₃ ] ^_ , [CH ₃ OS0 ₃ ] ^_ , [C ₂ H ₅ OS0 ₃ ]-, [CeFjSOa]-, [(BuO) ₂ P(0)0] ^" [CH ₃ C ₆ H ₄ S0 ₃ ] ^" , [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N] ^~ [C ₂ F ₅ S0 ₃ ]- [(C ₂ F ₅ S0 ₂ ) ₂ N)]-, [P(C ₂ F ₅ ) ₃ F ₃ ]- [B(CN) ₄ ]-, and [N(CN) ₂ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ o alkyl, substituted Ci-20 alkyl, C ₂ . ₂₀ alkenyl, and aryl;

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂ o alkyl, substituted C io alkyl, C ₂ _ ₂ o alkenyl, and aryl; and

the anion, X ^q_ , is selected from Br ^" , Γ, [N0 ₃ ] ^~ , [PF ₆ ] ^_ , [SnCl ₃ ] ^" , [SCN] ^" , [NCO]-, [CF ₃ S0 ₃ ]-, [CH ₃ OS0 ₃ ] ^" , [C2H5OSO3]-, [CeFjSOj] ^" , [(BuO) ₂ P(0)0]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ Nr, [C ₂ F ₅ S0 ₃ ] , [(C ₂ F ₅ S0 ₂ ) ₂ N)]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [B(CN) ₄ ] ^" , and [N(CN) ₂ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂ o alkyl, substituted Ci_ ₂₀ alkyl, and C ₂ . ₂₀ alkenyl;

R ⁴ and R ⁶ are each independently selected from C ₂ - ₂₀ alkyl, substituted Ci_ ₂₀ alkyl, and C ₂ _ ₂₀ alkenyl; and the anion, X ^q , is selected from Br , [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCN] ^{^} , [CF ₃ S0 ₃ ] , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ]-,

[C ₆ F ₅ S0 ₃ ]-, [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]- [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ] ^"

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, substituted Ci _-6 alkyl, and C _2-6 alkenyl;

R ⁴ and R ⁶ are each independently selected from C ₂ - ₂ o alkyl, substituted Ci_ ₆ alkyl, and C _2-6 alkenyl; and the anion, X ^q~ , is selected from Br ^" , [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCN] ^~ , [CF ₃ S0 ₃ ] ^~ , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ]- [C ₆ F ₅ S0 ₃ ]- [CH ₃ C6H ₄ S03]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and rN(CN) ₂ r.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci_ ₂₀ alkyl, hydroxy C e alkyl, carboxyl Ci. ₆ alkyl, and C ₂ .e alkenyl;

R ⁴ and R ⁶ are each independently selected from C ₂ . ₂ o alkyl, hydroxy Ci_ ₆ alkyl, carboxyl Ci_ ₆ alkyl, and C2-6 alkenyl; and

the anion, X ^q_ , is selected from Br ^" , [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCN] ^" [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" [C ₂ H ₅ OS0 ₃ ]-,

[C ₆ F ₅ S0 ₃ ]- [CH ₃ C6H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N] ^" [C ₂ F ₅ S0 ₃ r, [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ]-.

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, Ci _-20 alkyl, hydroxy Ci-6 alkyl, and C ₂ . ₆ alkenyl;

R ⁴ and R ⁶ are each independently selected from C _2-2 o alkyl, hydroxy Ci _-6 alkyl, carboxyl Ci_ ₆ alkyl, and C ₂ -6 alkenyl; and

the anion, X ^q~ , is selected from Br ^" , [N0 ₃ ] ^" , [PF ₆ ] ^_ , [SCN] ^" , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ] ^~

[C ₆ F ₅ S0 ₃ ]-, [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N] ^" [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" and [N(CN) ₂ ]-. In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, methyl, ethyl, w-propyl, wo-propyl, w-butyl, n-pentyl, n-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R ⁴ and R ⁶ are each independently selected from ethyl, w-propyl, wo-propyl, w-butyl, «-pentyl, ra-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, l-carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; or

R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl; and the anion, X ^q" , is selected from F ^" , Br ^" , I ^" , [N0 ₃ ] ^~ [SnCl ₃ ] ^" , [SCN] , [NCO] ^_ , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [(BuO) ₂ P(0)0]- _s [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [P(C ₂ F ₅ ) ₃ F ₃ ] ^" , [B(CN) ₄ ]- and [N(CN) ₂ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, methyl, ethyl, w-propyl, zjo-propyl, «-butyl, «-pentyl, «-hexyl, decyl, stearyl, 2-hydroxyethyl, allyl, and phenyl; and R ⁴ and R ⁶ are each independently selected from ethyl, n-propyl, zjo-propyl, H-butyl, «-pentyl, rc-hexyl, decyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, 1 -carboxyl-2-hydroxypropyl, 1 -carboxyl-2-methylpropyl, allyl, and phenyl; and

the anion, X ^_ , is selected from F ^" , Br ^" , Γ, [N0 ₃ ] ^" , [SnCl ₃ ] ^~ , [SCN] ^" , [NCO]-, [CF ₃ S0 ₃ ] ^_ , [CH ₃ OS0 ₃ ] ^~ [(BuO) ₂ P(0)0]-, [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]- [P(C ₂ F ₅ ) ₃ F ₃ ] [B(CN) ₄ ] , and [N(CN) ₂ ] ^" .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, methyl, ethyl, n-propyl, wo-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and

R ⁴ and R ⁶ are each independently selected from ethyl, «-propyl, wo-propyl, H-butyl, «-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and

the anion, X ^{q ~} is selected from F ^" , Br ^" , [N0 ₃ ] ^~ , [SCN] ^" , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^_ , [CH ₃ C ₆ H ₄ S0 ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^_ and [N(CN) ₂ ] ^_ .

In some embodiments, R ¹ , R ² , R ³ and R ⁵ are each independently selected from -H, methyl, ethyl, n-propyl, zjo-propyl, «-butyl, «-hexyl, stearyl, 2-hydroxyethyl, and allyl; and

R ⁴ and R ⁶ are each independently selected from ethyl, ^-propyl, wo-propyl, «-butyl, n-hexyl, stearyl, 2-hydroxyethyl, 1 -carboxylethyl, and allyl; and

the anion, X ^q~ , is selected from F ^~ , Br ^" , [N0 ₃ ] ^" , [SCN] ^" [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^~ , [CH ₃ C ₆ H ₄ S0 ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N]- and [N(CN) ₂ ] ^" .

In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are -H and R ² , R ⁴ and R ⁶ are phenyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are z ^' sopropyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl, R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are -H,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl,

R', R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-hydroxypropyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-methylpropyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are

2- carboxylpyrrolidinyl, and

the anion, X ^q~ is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^~ , [SCN] ^" , [NCOf, [N0 ₃ ] [AIC ] ^" , [A1 ₂ C1 ₇ ] ^~ [PF ₆ ] ^~

[SeCN] ^" , [CF ₃ SO ₃ ] ^" , [FHOMef, [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^~ , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)Or,

[CH ₃ C ₆ H4S03] ^~ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate,

3- fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ Nr, [(CF ₃ S0 ₂ )NC(0)CF ₃ ]- [(FS0 ₂ ) ₂ N] ^" [CF ₃ CF ₂ S0 ₃ r, [C ₄ F ₉ S0 ₃ ]-, [(CF ₃ CF ₂ S0 ₂ ) ₂ N)]- [(CF ₃ S0 ₂ ) ₃ C]- [(FS0 ₂ ) ₃ C]- [P(C ₂ F ₅ )3F ₃ ]-, [(CF ₃ ) ₂ P(0)Or, [(C ₂ F ₅ ) ₂ P(0)0]-, [(CF ₃ 0) ₂ P(0)0]- [(C ₂ F ₅ 0) ₂ P(0)0]- [BF ₃ (CF ₃ )3]-, [BF ₃ (C ₂ F ₅ )3]- [BF ₃ (CN)r, [B(CN) ₄ ]-, [N(CN) ₂ ] ^" and [C(CN) ₃ ]-.

In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are z ^' so-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl, and

the anion, X ^{q "} is selected from IT, Br ^" , Γ, [HF ₂ ] ^~ , [SCN] ^~ , [NCO] ^" [N0 ₃ ] ^" , [AICU]-, [AI2CI7] ^" , [PF ₆ ] ^" , [SeCN] ^" , [CF3SO3] ^" , [FHOMe] ^" , [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^" , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^" [(CF ₃ S0 ₂ )NC(0)CF ₃ ]-, [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ r, [C^SO,]-, [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" , [(CF ₃ S0 ₂ ) ₃ C] ^" , [(FS0 ₂ ) ₃ C]-, [P(C ₂ F ₅ ) ₃ F ₃ ] ^" , [(CF ₃ ) ₂ P(0)0] ^" , [(C ₂ F ₅ ) ₂ P(0)0] ^" _; [(CF ₃ 0) ₂ P(0)0] ^"

[(C ₂ F ₅ 0) ₂ P(0)0]- [BF ₃ (CF ₃ )3]-, [BF ₃ (C ₂ F ₅ ) ₃ ]-, [BF ₃ (CN)] ^" , [B(CN) ₄ ]-, [N(CN) ₂ r, and [C(CN) ₃ ] ^" In some embodiments,

R'-R ⁶ are 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are ώο-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl, and

the anion, X ^q" is selected from F ^" , Br ^" , Γ, [HF ₂ ] ^~ [SCN]-, [NCO] ^" , [N0 ₃ ] ^" , [AICU] ^" , [AI2CI7] ^" , [PF ₆ ] ^" , [SeCN] ^" , [CF ₃ S0 ₃ ] ^" , [FHOMe] ^" , [FHOEt] ^" , [FHOPr] ^" , [MeOS0 ₃ ] ^~ , [EtOS0 ₃ ] ^" , [(BuO) ₂ P(0)0] ^" , [CH ₃ C6H ₄ S03] ^~ , ((4-methylpiperazinyl)methyl)trifluoroborate, 2,3-difluoropyridine-4-trifluoroborate, 3-fluoropyridine-4-trifluoroborate, 5-methylfuran-2-trifluoroborate,

[2-(trimethylsilyl)ethoxy]methyltrifluoroborate, [BrCH ₂ BF ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ Nr, [(CF ₃ S0 ₂ )NC(0)CF ₃ ] , [(FS0 ₂ ) ₂ N] ^" , [CF ₃ CF ₂ S0 ₃ ] ^" , [C^SO,] ^" , [(CF ₃ CF ₂ S0 ₂ ) ₂ N)] ^" , [(CF ₃ S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C] ^" , [P(C ₂ F ₅ ) ₃ F ₃ ] ^" , [(CF ₃ ) ₂ P(0)0] ^" , [(C ₂ F ₅ ) ₂ P(0)0] ^" , [(CF ₃ 0) ₂ P(0)0]-,

[(C ₂ F ₅ 0) ₂ P(0)0] ^" , [BF ₃ (CF ₃ ) ₃ ] ^" , [BF ₃ (C ₂ F ₅ ) ₃ ] ^" , [BF ₃ (CN)] ^" , [B(CN) ₄ ] ^" , [N(CN) ₂ ] ^" , and [C(CN) ₃ ] ^" .

In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are -H and R ² , R ⁴ and R ⁶ are phenyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are iso-propyl, R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R\ R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are -H,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ^L , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is l-carboxyl-2-hydroxypropyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is l-carboxyl-2-methylpropyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are

2-carboxylpyrrolidinyl, and

the anion, X ^q~ , is selected from Br ^" , Γ, [N0 ₃ ] ^" , [PF ₆ ] ^~ , [SnCl ₃ ] ^~ , [SCN] ^" , [NCO]-, [CF ₃ S0 ₃ ] ^~ , [CH ₃ OS0 ₃ r, [C ₂ H ₅ OS0 ₃ ]- [CeFsSO,]- [(BuO) ₂ P(0)0] , [CH ₃ C ₆ H ₄ S0 ₃ ] ^' [(CF ₃ S0 ₂ ) ₂ N] , [(FS0 ₂ ) ₂ N] , [C ₂ F ₅ S0 ₃ ] ^~ , [(C ₂ F ₅ S0 ₂ ) ₂ N)]- [P(C ₂ F ₅ ) ₃ F ₃ ]-, [B(CN) ₄ r, and [N(CN) ₂ ] ^~ . In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are -H and R ² , R ⁴ and R ⁶ are phenyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are zso-propyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are -H,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is hexyl, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1-carboxylethyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-hydroxypropyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-methylpropyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are 2-carboxylpyrrolidinyl, and

the anion, X" ^' , is selected from ΒΓ, [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCNf, [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^~ , [C ₂ H ₅ OS0 ₃ ] ^_ , [C ₆ F ₅ S0 ₃ ]-, [CH ₃ C6H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N] ^" [C ₂ F ₅ S0 ₃ ] ^" , [(C ₂ F ₅ S0 ₂ ) ₂ N)r and [N(CN) ₂ ] ^' .

In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are fso-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl, and

the anion, X ^q" , is selected from Br ^" , [Ν0 ₃ Γ, [PF ₆ ] ^~ [SCN] ^~ [CF ₃ SO,] ^" , [CH ₃ OS0 ₃ ] ^_ , [C ₂ H ₅ OS0 ₃ ] ^~ , [C ₆ F ₅ S0 ₃ ]-, [CH ₃ C ₆ H ₄ S0 ₃ ]- [(CF ₃ S0 ₂ ) ₂ N]- [(FS0 ₂ ) ₂ N] ^" [C ₂ F ₅ S0 ₃ ]- [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ] ^" .

In some embodiments,

R'-R ⁶ are 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1-carboxylethyl, and the anion, X ^q" is selected from Br-, [NOj] ^" , [PF ₆ ] ^' , [SCN] ^" , [CF ₃ SO ₃ ] ^" , [CH ₃ OSO ₃ ] ^" , [C ₂ H ₅ OSO ₃ ]-, [C ₆ F ₅ S0 ₃ ]-, [CH _J C^SO _J ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N] ^" [C ₂ F ₅ S0 ₃ ]- [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ] ^" .

In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, pentyl, hexyl, decyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are -H and R ² , R ⁴ and R ⁶ are phenyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are wo-propyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are -H,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-hydroxypropyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxyl-2-methylpropyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, and R ⁵ and R ⁶ , together with the nitrogen atom to which they are attached, are

2-carboxylpyrrolidinyl, and

the anion, X ^q" , is selected from F ^" , Br ^" , Γ, [Ν0 ₃ Γ, [SnCl ₃ ] ^" , [SCN] ^" , [NCO] ^" , [CF ₃ SO ₃ ] , [CH ₃ OS0 ₃ ] ^" ,

[(BuO) ₂ P(0)0] ^" [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [P(C ₂ F ₅ ) ₃ F ₃ ]-, [B(CN) ₄ ]-, and [N(CN) ₂ ] ^" .

In some embodiments,

R'-R ⁶ are identical and are ethyl, propyl, butyl, allyl or 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R ¹ , R ² , R ³ and R ⁴ are wo-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl, R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1-carboxylethyl, and

the anion, X" ^" is selected from F ^" , Br ^" , [N0 ₃ ] ^" , [SCN] ^~ , [CF ₃ S0 ₃ ] ^~ , [CH ₃ OS0 ₃ ] ^~ ,

[(CF ₃ S0 ₂ ) ₂ N]- and [N(CN) ₂ ] ^" .

In some embodiments,

R'-R ⁶ are 2-hydroxyethyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are butyl,

R ¹ , R ³ and R ⁵ are methyl and R ² , R ⁴ and R ⁶ are stearyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are allyl,

R', R ² , R ³ and R ⁴ are iso-propyl and R ⁵ and R ⁶ are butyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl and R ⁵ and R ⁶ are 2-hydroxyethyl,

R ³ , R ⁴ , R ⁵ and R ⁶ are ethyl and R ¹ and R ² are methyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is methyl and R ⁶ is hexyl,

R ¹ , R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is butyl, or

R', R ² , R ³ and R ⁴ are ethyl, R ⁵ is hydrogen and R ⁶ is 1 -carboxylethyl, and

the anion, X ^{q "} is selected from F ^" , Br-, [N0 ₃ ] ^" , [SCN] ^" , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [CH ₃ C ₆ H ₄ S0 ₃ ] ^" ,

[(CF ₃ S0 ₂ ) ₂ N] ^" and [N(CN) ₂ ] ^_ .

In some embodiments, the compound is selected from the group consisting of:

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethyIamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium/>-toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide; (22) tris(dibutylamino)cyclopropenium nitrate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(26) tris(diethanolamino)cyclopropenium fluoride;

(28) tris(diallylamino)cyclopropenium bromide;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41 ) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; (68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(69) tris(dipentylamino)cyclopropeniuni dicyanoamide;

(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(76) bis(di 5o-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;

(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;

(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(80) bis(diethylamino)aminocyclopropenium methylsulfate;

(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide;

(86) bis(diethylamino)dihexylaminocyclopropenium iodide;

(87) tris(dimethylamino)cyclopropenium dicyanoamide;

(88) tris(dimethylamino)cyclopropenium thiocyanate;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;

(91) tris(dihexylamino)cyclopropenium dibutylphosphate;

(92) bis(diethylamino)-5-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;

(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;

(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(99) tris(dibutylamino)cyclopropenium isocyanate;

(100) tris(dibutylamino)cyclopropenium trichlorostannate;

(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;

(102) bis(diethylamino)di 0-propylaminocyclopropenium methylsulfate;

(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;

(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is selected from the group consisting of compounds (4)-(6), (8)-(10), (12)-(16), (19)-(22), (24), (26), (28)-(30), (32)-(34), (36), and (38)-(64). In one embodiment, the compound is selected from the group consisting of compounds (68), (69), (71), (72), (74)-(82), (84)-(103), and (105)-(107).

In some embodiments, the compound is selected from the group consisting of:

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium/?-toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(20) tris(dibutylamino)cyclopropenium bromide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(26) tris(diethanolamino)cyclopropenium fluoride;

(28) tris(diallylamino)cyclopropenium bromide;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylarm^ocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide; (46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide; and

(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate.

In a second aspect, the present invention provides a compound of formula [Y ⁺ ] _q [X ^q" ] wherein q is 1 ; wherein the cation, is selected from

tris(dipropylamino)cyclopropenium,

tris(dibutylamino)cyclopropenium,

tris(dipentylamino)cyclopropenium,

tris(dihexylamino)cyclopropenium,

tris(didecylamino)cyclopropenium,

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(hexylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(diwo-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)dipropylaminocyclopropenium,

bis(diethylamino)diiio-propylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium,

bis(diethylamino)octadecylmethylaminocyclopropenium,

bis(diethylamino)dimethylaminocyclopropenium, and

bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium; and

wherein the anion, X ^q~ is selected from CI ^" Br ^" [BF ₄ ] ^" , [N0 ₃ ] ^" , ( F ₆ ] ^" , [SCN] ^" , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ]-, [C^sSO,]-, [CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ ]- [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" and [N(CN) ₂ ]-.

In some embodiments, the cation, Y ^1" , is selected from

tris(dipropylamino)cyclopropenium,

tris(dibutylamino)cyclopropenium,

tris(dipentylamino)cyclopropenium,

tris(dihexylamino)cyclopropenium,

tris(didecylamino)cyclopropenium,

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(diwo-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)diwo-propylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium,

bis(diethylamino)hexylmethylaminocyclopropenium, and

bis(diethylamino)dimethylaminocyclopropenium. In some embodiments, the cation, Y ^1" , is selected from

tris(dipropylamino)cyclopropenium,

tris(dibutylamino)cyclopropenium,

tris(dihexylamino)cyclopropenium,

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(hexylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(dii5O-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)dipropylaminocyclopropenium,

bis(diethylamino)diwo-propylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium, bis(diethylamino)dihexylaminocyclopropenium, bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium, bis(diethylamino)octadecylmethylaminocyclopropenium, bis(diethylamino)dimethylaminocyclopropenium, and bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium.

In some embodiments, the cation, Y^, is selected from tris(dipropylamino)cyclopropenium,

tris(dibutylamino)cyclopropenium,

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(diwo-propylamino)dibutylaminocyclopropenium, bis(diethylamino)dibutylaminocyclopropenium, bis(diethylamino)dihexylaminocyclopropenium, bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium, and bis(diethylamino)dimethylaminocyclopropenium.

In some embodiments, the cation, Y , is selected from tris(dipropylamino)cyclopropenium,

tris(dibutylamino)cyclopropenium,

tris(dihexylamino)cyclopropenium,

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(hexylmethylamino)cyclopropenium,

bis(diethylamino)dipropylaminocyclopropenium, bis(diethylamino)dibutylaminocyclopropenium, bis(diethylamino)dihexylaminocyclopropenium, bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium, bis(diethylamino)hexylmethylaminocyclopropenium, bis(diethylamino)octadecylmethylaminocyclopropenium, bis(diethylamino)dimethylaminocyclopropenium, and bis(diethylamino)di(2-methoxyethyl)aminocyclopropenium. In some embodiments, the cation, is selected from

tris(dipropylamino)cyclopropenium,

tris(dibutylamino)cyclopropenium,

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium,

bis(diethylamino)hexylmethylaminocyclopropenium, and

bis(diethylamino)dimethylaminocyclopropenium.

In some embodiments, the cation, is selected from

tris(butylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(diwo-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)butylmethylaminocyclopropenium,

bis(diethylamino)hexylmethylaminocyclopropenium, and

bis(diethylamino)dimethylaminocyclopropenium; and

the anion, X ^q~ , is selected from CI ^' , Br ^" , [BF ₄ ] ^~ , [Ν0 ₃ Γ, [PF ₆ ] ^" [SCNf, [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" ,

[C ₂ H ₅ OS0 ₃ ] - [C ₆ F ₅ S0 ₃ ]-, [CH3C6H4SO3] ^" , [(CF ₃ S0 ₂ ) ₂ Nr, [(FS0 ₂ ) ₂ N] , [C ₂ F ₅ S0 ₃ ] , [(C ₂ F ₅ S0 ₂ ) ₂ N)r and [N(CN) ₂ ]-. In some embodiments, the cation, Y\ is selected from

tris(diallylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(di 5O-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)hexylmethylaminocyclopropenium, and

bis(diethylamino)dimethylaminocyclopropenium; and the anion, X ^q" is selected from CI ^" , Br ^" , [BF ₄ ] ^~ , [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCN] ^" , [CF ₃ SO3] ^" , [CH ₃ OSO ₃ ] ^" ,

[C2H5OSO3]-, [C6F5SO3]- [CH ₃ C6H4S03] ^" , [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ r, [(C ₂ F ₅ S0 ₂ ) ₂ N)r and [N(CN) ₂ ]-.

In some embodiments, the cation, Y ^"1" , is selected from

tris(butylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(diwo-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)hexylmethylaminocyclopropenium, and

bis(diethylamino)dimethylaminocyclopropenium; and

the anion, X ^q" is selected from CI ^" , Br ^" , [BF ₄ ] ^" , [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCN] ^" , [CF ₃ SO ₃ ] ^" , [CH3OSO ₃ ] ^" ,

[C ₂ H ₅ OS0 ₃ ] ^" , [C^SC^] ^" , [CH ₃ C ₆ H ₄ S03] ^" , [(CF ₃ S0 ₂ ) ₂ N] ^" , [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ r, [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" and [N(CN) ₂ ] ^" .

In some embodiments, the cation, Y ^" \ ^' is selected from

tris(dipentylamino)cyclopropenium,

tris(didecylamino)cyclopropenium,

tris(butylmethylamino)cyclopropenium,

tris(octadecylmethylamino)cyclopropenium,

bis(dit5o-propylamino)dibutylaminocyclopropenium,

bis(diethylamino)dibutylaminocyclopropenium,

bis(diethylamino)diwo-propylaminocyclopropenium,

bis(diethylamino)dihexylaminocyclopropenium,

bis(diethylamino)diallylaminocyclopropenium,

bis(diethylamino)hexylmethylaminocyclopropenium, and

bis(diethylamino)dimethylaminocyclopropenium; and

the anion, X ^q" is selected from CI ^" , Br ^" , [BF ₄ ] ^" , [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCN] ^" , [CF3SO3] ^" , [CH3OSO3] ^" ,

[C ₂ H ₅ OS0 ₃ ] ^" , [C ₆ F ₅ S0 ₃ ] ^" , [(CF ₃ S0 ₂ ) ₂ N] ^" , [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ ] ^" , [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" and [N(CN) ₂ ] ^" .

In a third aspect, the present invention provides a compound of formula [Y ⁺ ] _q [X ^q ] wherein q is 1 ;

wherein the cation, is tris(diethylamino)cyclopropenium; and

wherein the anion, X ^q" is selected from Γ, [BF ₄ ] ^" [N0 ₃ ] ^" , [PF ₆ ] ^" , [SCN] ^" , [CF ₃ SO ₃ ] ^" , [CHJOSOJ] ^" ,

[C ₂ H ₅ OS0 ₃ ] ^" [C ₆ F ₅ S0 ₃ ]- [(CF ₃ S0 ₂ ) ₂ N] ^" , [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ ] ^" [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" and [ (CN) ₂ ]-. In some embodiments, the anion, X ^q" , is selected from [BF ₄ ] ^~ , [N0 ₃ ] ^_ , [PF ₆ ] ^~ , [SCN] ^" , [CF ₃ S0 ₃ ] ^~ ,

[CH ₃ OS0 ₃ r, [C ₂ H ₅ OS0 ₃ ]-, [C ₆ F ₅ S0 ₃ ]- [CH.C^SO,] ^" [(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N] ^~ [C ₂ F ₅ S0 ₃ ]-,

[(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ]-.

In a fourth aspect, the present invention provides a compound of formula [Y^ _q fX ^11" ] wherein q is 1 ;

wherein the cation, Y ^1" , is selected from

bis(diethylamino)aminocyclopropenium,

bis(diethylamino)butylaminocyclopropenium,

bis(diethylamino)hexylaminocyclopropenium,

bis(diethylamino)diethanolaminocyclopropenium,

tris(diethanolamino)cyclopropenium,

trisanilinocyclopropenium,

bis(diethylamino)-iS'-(l -carboxylethylamino)cyclopropenium,

bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,

bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and

bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium; and

wherein the anion, X ^q" , is selected from [BF ₄ ] ^~ , [PF ₆ ] ^" , [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ] ^" , [C ₆ F ₅ S0 ₃ ]\ [CH^^SO,] ^" [(CF ₃ S0 ₂ ) ₂ N]- [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ r, [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ] ^"

In some embodiments, the cation, Y ^1" , is selected from

bis(diethylamino)aminocyclopropenium,

bis(diethylamino)butylaminocyclopropenium,

bis(diethylamirio)hexylaminocyclopropenium,

trisanilinocyclopropenium,

bis(diethylamino)-5-( 1 -carboxylethylamino)cyclopropenium,

bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,

bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and

bis(diethylamino)-5-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.

In some embodiments, the cation, Y ^1" , is selected from

bis(diethylamino)butylaminocyclopropenium,

bis(diethylamino)hexylaminocyclopropenium,

trisanilinocyclopropenium,

bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium,

bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,

bis(diethylamino)-S-(l-carboxy-2-methylpropylamino)cyclop ropenium, and

bis(diethylamino)-S-(l-carboxy-2-hydroxylpropylamino))cyc lopropenium. In some embodiments, the cation, Y ^"1" , is selected from

bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium,

bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,

bis(diethylamino)-S-(l-carboxy-2-methylpropylamino)cyclop ropenium, and

bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.

In some embodiments, the cation, Y^, is selected from

bis(diethylamino)aminocyclopropenium,

trisanilinocyclopropenium,

bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,

bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and

bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.

In some embodiments, the cation, Y^, is selected from

bis(diethylamino)aminocyclopropenium,

bis(diethylamino)hexylaminocyclopropenium,

trisanilinocyclopropenium,

bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium,

bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium, and

bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium.

In some embodiments, the cation, Y ^"1" , is selected from

bis(diethylamino)butylaminocyclopropenium,

bis(diethylamino)hexylaminocyclopropenium,

bis(diethylamino)diethanolaminocyclopropenium,

tris(diethanolamino)cyclopropenium, and

bis(diethylamino)-5-( 1 -carboxylethylamino)cyclopropenium. In some embodiments, the cation, Y^, is selected from

bis(diethylamino)butylaminocyclopropenium,

bis(diethylamino)diethanolaminocyclopropenium,

tris(diethanolamino)cyclopropenium, and

bis(diethylamino)-5-( 1 -carboxy lethylamino)cyclopropenium. In some embodiments, the cation, Y ⁺ , is bis(diethylamino)aminocyclopropenium.

In some embodiments, the cation, Y is trisanilinocyclopropenium.

In a fifth aspect, the present invention provides a compound of formula [Y ⁺ ] _q [X ^q" ] wherein q is 1 or 2; wherein the cation, Y\ is a triaminocyclopropenium ion of the formula (II):

wherein the anion, X ^q~ , is selected from [SCN] ^~ , [CF ₃ SO ₃ ]-, [FHO(C,_ ₆ alkyl)] ^" , [(C,. ₆ alkyl)OS0 ₃ ] ^" , [C ₆ F ₅ S0 ₃ ]-, [(C,. ₆ alkyl)(C,. ₆ alkyl)P(0)Or, [CH^^SCy ^" , [Co(C ₂ B ₉ H„)2r, [C ₂ B ₉ H ₁₂ ]-, [B ₁₀ Cl ₁₀ [B ₁₂ C1 ₁₂ ] ² - [CB„H ₁₂ r, P ₁₂ H„N(C _W alkyl),] ^" [(C,_ ₆ alkyl)SnB„H„r, [R ^B CB„R ^c ₅ X ^B 6r, [R°BF ₃ ] , [(CF ₃ S0 ₂ ) ₂ N]- [(CF ₃ S0 ₂ )NC(0)CF ₃ ]- [(FS0 ₂ ) ₂ N]-, [R ^F CF ₂ S0 ₃ r, [(R ^G S0 ₂ ) ₂ N)] ^" [(R ^G S0 ₂ ) ₃ C] ^' ,

[(FS0 ₂ ) ₃ Cr [R ^F CF ₂ C(0)0]-, [P(C _n F _2n+1 . _m H _m ) _y F _6-y ]-, [PiC^)^.^, [R ^F ₂ P(0)0] ^" , [R ^F P(0)0 ₂ ] ^2"

[BF,R ^F 4_J-, ^J ; and wherein R ^B , R ^c , R ^D , X ^B , R ^F , R°, n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.

In some embodiments, wherein the cation, is tris(dimethylamino)cyclopropenium, the anion, X ^q~ , selected from [SCN] ^" [CF ₃ S0 ₃ ] ^" , [CH ₃ OS0 ₃ ] , [C ₂ H ₅ OS0 ₃ ] , [C ₆ F ₅ S0 ₃ ] , [CH ₃ C ₆ H ₄ S0 ₃ ] ^~

[(CF ₃ S0 ₂ ) ₂ N]-, [(FS0 ₂ ) ₂ N]-, [C ₂ F ₅ S0 ₃ ]-, [(C ₂ F ₅ S0 ₂ ) ₂ N)]- and [N(CN) ₂ ]-.

In another embodiment, the compound is selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide

(87) tris(dimethylamino)cyclopropenium dicyanoamide; and

(88) tris(dimethylamino)cyclopropenium thiocyanate.

In one embodiment, the compound is compound (2). In another embodiment, the compound is compound (87) or (88).

In a sixth aspect, the present invention provides a compound of formula [Y ⁺ ] _q [X ^q" ] wherein q is 1 or 2; wherein the cation, Y ^* , is a triaminocyclopropenium ion of the formula (III):

wherein R ⁷ is methyl and R ⁸ is selected from C2-20 alkyl, substituted Ci. ₂₀ alkyl, C ₂ . ₂₀ alkenyl, substituted C2-20 alkenyl, C2-20 alkynyl, substituted C ₂ . ₂ o alkynyl, C ₃ .i ₀ cycloalkyl, substituted C3.10 cycloalkyl, C ₃ .i ₀ cycloalkenyl, substituted C _3- i ₀ cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl; or

R ⁷ and R ⁸ are each independently selected from C ₂ - ₂ o alkyl, substituted Cj_ ₂ o alkyl, C ₂ .2o alkenyl, substituted C ₂ - ₂ o alkenyl, C2-20 alkynyl, substituted C2-20 alkynyl, C ₃ _i ₀ cycloalkyl, substituted C ₃ _io cycloalkyl, C ₃ . ₁₀ cycloalkenyl, substituted C ₃ .| ₀ cycloalkenyl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, aryl, and substituted aryl;

wherein the anion, X ^q~~ , is selected from [SCN]-, [CF ₃ COO] ^_ , [SeCN]-, [CF ₃ S0 ₃ r, [FHO(C,. ₆ alkyl)] ^" , [(C _1-6 alkyl)OS0 ₃ ]-, [C^SO,] ^' , [(C,_ ₆ alkyl)(C,_ ₆ alkyl)P(0)0]- [CH ₃ C ₆ H ₄ S0 ₃ ]-, [Co(C ₂ B ₉ Hn)2] ^" , [C ₂ B ₉ H ₁₂ r, [B ₁₀ C1 ₁₀ ] ^2' , [B ₁₂ C1 ₁₂ ] ² - [CB _u H ₁₂ r, alkyl),] ^" , [(C,_ ₆ alkyl)SnB„H„r,

[R ^B CB„R ^c ₅ X ^B 6r, [R ^D BF ₃ ] ^~ , [(CF ₃ S0 ₂ ) ₂ N]-, [(CF ₃ S0 ₂ )NC(0)CF ₃ ]- [(FS0 ₂ ) ₂ Nr, [R ^F CF ₂ S0 ₃ r,

[(R ^G S0 ₂ ) ₂ N)]- [(R ^G S0 ₂ ) ₃ C]-, [(FS0 ₂ ) ₃ C]-, [R ^F CF ₂ C(0)0]- [P(C _n F _2n+1 . _m H _m ) _y F ₆ . _y ]-, [P(C ₆ F ₅ ) _y F ₆ . _y ]- [R ^F P(0)0] - [R ^F P(0)0 ₂ ] ² -, [BF _z R ^F 4-z]- [BF ₂ (CN) ₄ . _Z ]- [N(CF ₃ ) ₂ ] ^~ , [N(CN) ₂ ] ^" , [C(CN) ₃ ] ^" and

wherein R ^B , R ^c , R ^D , X ^B , R ^F , R ^G , n, m, y, z, -Z-, and -Y- are as defined for the compounds of the first aspect.

In some embodiments, R ₇ is methyl and R ₈ is butyl, R ₇ is methyl and R ₈ is hexyl, R ₇ is methyl and R ₈ is stearyl, R ₇ and R ₈ are ethyl, R ₇ and R ₈ are propyl, R ₇ and R ₈ are butyl, or R ₇ and R ₈ are hexyl.

In some embodiments, the cation, Y ^" , is selected from

bis(dimethylamino)hexylmethylaminocyclopropenium,

bis(dimethylamino)dihexylaminocyclopropenium, and

bis(dimethylamino)dibutylaminocyclopropenium. In some embodiments, the cation, Y ⁴ , is selected from bis(dimethylamino)hexylmethylaminocyclopropenium,

bis(dimethylamino)dihexylaminocyclopropenium,

bis(dimethylamino)dibutylaminocyclopropenium; and

the anion, X ^q" is selected from [SCN] ^" , [CF3SO ₃ ] ^" , [CH ₃ OS0 ₃ ] ^" , [C ₂ H ₅ OS0 ₃ ]-, [CeFsSOa]-,

[CH ₃ C ₆ H ₄ S0 ₃ ]-, [(CF ₃ S0 ₂ ) ₂ N]- [(FS0 ₂ ) ₂ N] ^" , [C ₂ F ₅ S0 ₃ ] , [(C ₂ F ₅ S0 ₂ ) ₂ N)] ^" and [N(CN) ₂ ] ^"

In another embodiment, the compound is selected from the group consisting of:

(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In a seventh aspect, the present invention provides a compound selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium p-toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(11) tris(dipropylamino)cyclopropenium chloride;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(18) tris(dibutylamino)cyclopropenium chloride;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(26) tris(diethanolamino)cyclopropenium fluoride;

(27) tris(diallylamino)cyclopropenium chloride;

(28) tris(diallylamino)cyclopropenium bromide; (29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)arriide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61 ) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium methylsulfate;

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride; (67) tris(dipentylamino)cyclopropenium chloride;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(69) tris(dipentylamino)cyclopropenium dicyanoamide;

(70) tris(dihexylamino)cyclopropenium chloride;

(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide;

(73) tris(didecylamino)cyclopropenium chloride;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(76) bis(diwo-propylarruno)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;

(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;

(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(80) bis(diethylamino)aminocyclopropenium methylsulfate;

(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;

(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide;

(86) bis(diethylamino)dihexylaminocyclopropenium iodide;

(87) tris(dimethylamino)cyclopropenium dicyanoamide;

(88) tris(dimethylamino)cyclopropenium thiocyanate;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;

(91) tris(dihexylamino)cyclopropenium dibutylphosphate;

(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(95) bis(diethylamino)-5-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;

(96) bis(diethylamino)-S-(l-carboxy-2-methylpropylamino)cycloprop enium

bis(trifluoromethanesulfonyl)amide;

(97) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;

(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(99) tris(dibutylamino)cyclopropenium isocyanate;

(100) tris(dibutylamino)cyclopropenium trichlorostannate;

(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate; 102) bis(diethylamino)diwo-propylaminocyclopropenium methylsulfate;

103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;

105) bis(dimethylannno)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

106) bis(dimethylarnino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide. n one embodiment, the compound is selected from the group consisting of compounds (2), and (4)-(65). n one embodiment, the compound is selected from the group consisting of compounds (67)-(103), and 105)-(107). n one embodiment, the compound is selected from the group consisting of:

2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

5) tris(diethylamino)cyclopropenium dicyanoamide;

6) tris(diethylamino)cyclopropenium nitrate;

7) tris(diethylamino)cyclopropenium tetrafluoroborate;

8) tris(diethylamino)cyclopropenium thiocyanate;

9) tris(diethylamino)cyclopropenium p-toluenesulfonate;

10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

13) tris(dipropylamino)cyclopropenium dicyanoamide;

14) tris(dipropylamino)cyclopropenium fluoride diethanol;

15) tris(dipropylamino)cyclopropenium fluoride ethanol;

16) tris(dipropylamino)cyclopropenium nitrate;

17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

20) tris(dibutylamino)cyclopropenium bromide;

21) tris(dibutylamino)cyclopropenium dicyanoamide;

22) tris(dibutylamino)cyclopropenium nitrate;

23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

25) tris(diethanolamino)cyclopropenium chloride;

26) tris(diethanolamino)cyclopropenium fluoride;

28) tris(diallylamino)cyclopropenium bromide;

29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

30) tris(diallylamino)cyclopropenium dicyanoamide;

31) tris(butylmethylamino)cyclopropenium chloride;

32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)arnide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; and

(65) bis(dii5o-propylamino)dibutylaminocyclopropenium chloride.

In another embodiment, the compound is selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium/?-toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(20) tris(dibutylamino)cyclopropenium bromide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(26) tris(diethanolamino)cyclopropenium fluoride;

(27) tris(diallylamino)cyclopropenium chloride;

(28) tris(diallylamino)cyclopropenium bromide;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifiuoromethanesulfonyl)amide;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate; and

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride.

In another embodiment, the compound is selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(?) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium/ toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(20) tris(dibutylamino)cyclopropenium bromide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(26) tris(diethanolamino)cyclopropenium fluoride; (28) tris(diallylamino)cyclopropenium bromide;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S- ( 1 -carboxylethylamino)cyclopropenium methylsulfate; and

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride. In another embodiment, the compound is selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(44) bis(diethylamino)dibutylaminocyclopropemum bis(trifluoromethanesulfonyl)amide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;

(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(94) bis(diethylamino)-5-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is selected from the group consisting of compounds (2), (4), (12), (19), (29), (32), (38), (41), (44), (47), (50), (54), (56), (59), and (62). In another embodiment, the compound is selected from the group consisting of compounds (68), (71 ), (74), (76), (79), (81 ), (82), (92), (94), (96), (98), (105), (106), and (107). In another embodiment, the compound is selected from the group consisting of:

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(69) tris(dipentylamino)cyclopropenium dicyanoamide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(77) bis(di/5o-propylamino)dibutylaminocyclopropenium dicyanoamide;

(87) tris(dimethylamino)cyclopropenium dicyanoamide; and

(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide.

In one embodiment, the compound is selected from the group consisting of compounds (5), (13), (21), (30), (33), (39), (42), (45), (48), (57), (60), and (63). In another embodiment, the compound is selected from the group consisting of compounds (69), (72), (75), (77), (87), and (103).

In another embodiment, the compound is selected from the group consisting of:

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate; and

(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate.

In one embodiment, the compound is selected from the group consisting of compounds (7), (17), (23), and (35). In another embodiment, the compound is compound (83).

In another embodiment, the compound is selected from the group consisting of:

(6) tris(diethylamino)cyclopropenium nitrate;

(16) tr is(dipropylamino)cyclopropenium nitrate;

(22) tris(dibutylamino)cyclopropenium nitrate; and

(34) tris(butylmethylamino)cyclopropenium nitrate. In another embodiment, the compound is selected from the group consisting of:

(1 1 ) tris(dipropylamino)cyclopropenium chloride;

(18) tris(dibutylamino)cyclopropenium chloride;

(25) tris(diethanolamino)cyclopropenium chloride;

(27) tris(diallylamino)cyclopropenium chloride;

(31) tris(butylmethylamino)cyclopropenium chloride;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(65) bis(diwo-propylarnino)dibutylaminocyclopropenium chloride;

(67) tris(dipentylamino)cyclopropenium chloride;

(70) tris(dihexylamino)cyclopropenium chloride; and

(73) tris(didecylamino)cyclopropenium chloride.

In one embodiment, the compound is selected from the group consisting of compounds (1 1), (18), (25), (27), (31), (37), and (65). In another embodiment, the compound is selected from the group consisting of compounds (67), (70), and (73).

In another embodiment, the compound is selected from the group consisting of:

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate;

(53) bis(diethylamino)diallylaminocyclopropenium methylsulfate;

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;

(78) bis(diethylamino)hexylaminocyclopropenium methylsulfate;

(80) bis(diethylamino)aminocyclopropenium methylsulfate;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;

(97) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate; and

(102) bis(diethylamino)diwo-propylaminocyclopropenium methylsulfate.

In one embodiment, the compound is selected from the group consisting of compounds (40), (43), (46), (52), (53), (55), (58), (61), and (64). In another embodiment, the compound is selected from the group consisting of compounds (78), (80), (93), (95), (97), and (102).

In another embodiment, the compound is selected from the group consisting of: (14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(26) tris(diethanolamino)cyclopropenium fluoride; and

(51 ) bis(diethylamino)diethanolaminocyclopropenium fluoride. In another embodiment, the compound is selected from the group consisting of:

(8) tris(diethylamino)cyclopropenium thiocyanate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate; and

(88) tris(dimethylamino)cyclopropenium thiocyanate.

In one embodiment, the compound is compound (8) or (36). In another embodiment, the compound is compound (88).

In another embodiment, the compound is (20) tris(dibutylamino)cyclopropenium bromide or (28) tris(diallylamino)cyclopropenium bromide.

In another embodiment, the compound is selected from the group consisting of:

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate; and

(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate.

In one embodiment, the compound is compound (10) or (24). In another embodiment, the compound is compound (101).

In another embodiment, the compound is (9) tris(diethylamino)cyclopropenium /?-toluenesulfonate. In another embodiment, the compound is selected from the group consisting of:

(49) bis(diethylamino)diethanolamino-cyclopropenium iodide;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide; and

(86) bis(diethylamino)dihexylaminocyclopropenium iodide. In one embodiment, the compound is compound (49). In another embodiment, the compound is selected from the group consisting of compounds (84), (85), and (86).

In another embodiment, the compound is (89) tris(dibutylamino)cyclopropenium tetracyanoborate.

In another embodiment, the compound is (90) tris(dibutylamino)cyclopropenium

tris(pentafluoroethyl)trifluorophosphate.

In another embodiment, the compound is (91) tris(dihexylamino)cyclopropenium dibutylphosphate. In another embodiment, the compound is (99) tris(dibutylamino)cyclopropenium isocyanate.

In another embodiment, the compound is (100) tris(dibutylamino)cyclopropenium trichlorostannate.

In another embodiment, the compound is selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(87) tris(dimethylamino)cyclopropenium dicyanoamide; and

(88) tris(dimethylamino)cyclopropeniuni thiocyanate.

In one embodiment, the compound is compound (2). In another embodiment, the compound is compound (87) or (88).

In another embodiment, the compound is selected from the group consisting of:

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium /?-toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate; and

(85) tris(diethylamino)cyclopropenium iodide.

In one embodiment, the compound is selected from the group consisting of compounds (4)-(10). In another embodiment, the compound is compound (85).

In another embodiment, the compound is selected from the group consisting of:

(1 1) tris(dipropylamino)cyclopropenium chloride;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(14) tris(dipropylamino)cyclopropenium fluoride diethanol;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate; and

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate.

In another embodiment, the compound is selected from the group consisting of:

(18) tris(dibutylamino)cyclopropenium chloride;

( 19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(22) tris(dibutylamino)cyclopropenium nitrate; (23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate

(99) tris(dibutylamino)cyclopropenium isocyanate; and

(100) tris(dibutylamino)cyclopropenium trichlorostannate.

In one embodiment, the compound is selected from the group consisting of compounds (18)-(24). In another embodiment, the compound is selected from the group consisting of compounds (89), (90), (99), and (100).

In another embodiment, the compound is (25) tris(diethanolamino)cyclopropenium chloride or (26) tris(diethanolamino)cyclopropenium fluoride.

In another embodiment, the compound is selected from the group consisting of:

(27) tris(diallylamino)cyclopropenium chloride;

(28) tris(diallylamino)cyclopropenium bromide;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and

(30) tris(diallylamino)cyclopropenium dicyanoamide.

In another embodiment, the compound is selected from the group consisting of:

(67) tris(dipentylamino)cyclopropenium chloride;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and

(69) tris(dipentylamino)cyclopropenium dicyanoamide.

In another embodiment, the compound is selected from the group consisting of:

(70) tris(dihexylamino)cyclopropenium chloride;

(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide; and

(91) tris(dihexylamino)cyclopropenium dibutylphosphate.

In another embodiment, the compound is selected from the group consisting of:

(73) tris(didecylamino)cyclopropenium chloride;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and

(75) tris(didecylamino)cyclopropenium dicyanoamide.

In another embodiment, the compound is (82) trisanilinocyclopropenium

bis(trifluoromethanesulfonyl)amide.

In another embodiment, the compound is selected from the group consisting of: (31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)arnide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate; and

(36) tris(butylmethylamino)cyclopropenium thiocyanate.

In another embodiment, the compound is selected from the group consisting of:

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; and

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide.

In another embodiment, the compound is selected from the group consisting of:

(40) bis(diethylamino)dimethylaminocyclopropenium methylsulfate;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide.

In another embodiment, the compound is selected from the group consisting of:

(43) bis(diethylamino)dibutylaminocyclopropenium methylsulfate;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide; and

(84) bis(diethylamino)dibutylaminocyclopropenium iodide.

In one embodiment, the compound is selected from the group consisting of compounds (43)-(45). In another embodiment, the compound is compound (84).

In another embodiment, the compound is selected from the group consisting of:

(46) bis(diethylamino)dihexylaminocyclopropenium methylsulfate;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(86) bis(diethylamino)dihexylaminocyclopropenium iodide; and

(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate.

In one embodiment, the compound is selected from the group consisting of compounds (46)-(48). In another embodiment, the compound is compound (86) or (101).

In another embodiment, the compound is selected from the group consisting of:

(49) bis(diethylamino)diethanolaminocyclopropenium iodide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (51) bis(diethylamino)diethanolaminocyclopropenium fluoride; and

(52) bis(diethylamino)diethanolaminocyclopropenium methylsulfate.

In another embodiment, the compound is (53) bis(diethylamino)diallylaminocyclopropenium

methylsulfate or (54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In another embodiment, the compound is selected from the group consisting of:

(55) bis(diethylamino)butylmethylaminocyclopropenium methylsulfate;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide.

In another embodiment, the compound is selected from the group consisting of:

(58) bis(diethylamino)hexylmethylaminocyclopropenium methylsulfate;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide.

In another embodiment, the compound is selected from the group consisting of:

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide; and

(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate.

In one embodiment, the compound is selected from the group consisting of compounds (61 )-(63). In another embodiment, the compound is compound (83).

In another embodiment, the compound is (64) bis(diethylamino)-S-(l -carboxylethylamino)- cyclopropenium methylsulfate or (92) bis(diethylamino)-S-(l-carboxylethylamino)-cyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is compound (64). In another embodiment, the compound is compound (92).

In another embodiment, the compound is selected from the group consisting of:

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;

(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(77) bis(di/50-propylamino)dibutylaminocyclopropenium dicyanoamide.

In one embodiment, the compound is compound (65). In another embodiment, the compound is compound (76) or (77). In one embodiment, the compound is (78) bis(diethylamino)hexylaminocyclopropenium methylsulfate or (79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is (80) bis(diethylamino)aminocyclopropenium methylsulfate or (81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is (93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate or (94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium

bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is (95) bis(diethylamino)-S-(l-carboxy-2- methylpropylamino)cyclopropenium methylsulfate or (96) bis(diethylamino)-S-(l-carboxy-2- methylpropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is (97) bis(diethylamino)-S-(l-carboxy-2- hydroxylpropylamino)cyclopropenium methylsulfate or (98) bis(diethylamino)-S-(l-carboxy-2- hydroxylpropylamino))cyclopropemum bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is (102) bis(diethylamino)diz ^' so-propylamino-cyclopropenium methylsulfate or (103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide.

In one embodiment, the compound is (105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is (106) bis(dimethylamino)dihexylaminocyclopropenium

bis(trifluoromethanesulfonyl)amide.

In one embodiment, the compound is (107) bis(dimethylamino)dibutylaminocyclopropenium

bis(trifluoromethanesulfonyl)amide.

Preparation

Triaminocyclopropenium chloride salts wherein all six substituents are identical (R ⁶ = R ⁵ = R ⁴ = R ³ = R ² = R ¹ ), or wherein all three amino groups are identical (R ⁵ = R ³ = R ¹ and R ⁶ = R ⁴ = R ² ), can be synthesised from the appropriate secondary amine and either tetrachlorocyclopropene (Z. Yoshida and Y. Tawara, J. Am. Chem. Soc., 1971, 93, 2573, which is incorporated herein in its entirety by reference) or

pentachlorocyclopropane (M. J. Taylor, P. W. J. Surman and G. R. Clark, J. Chem. Soc, Chem.

Commun., 1994, 21, 2517, which is incorporated herein in its entirety by reference). Generally, a larger amount of the amine is required for those reactions using pentachlorocyclopropane. An excess of amine may be used as a base to remove the HC1 generated during the reaction. These synthetic methods are particularly useful to prepare salts with hydrophobic anions, such as

[CF ₃ SO ₃ ] ^" , Γ, [I ₃ ] and [BF ₄ ] ^~ , but are not limited thereto, because the salt can be extracted into an organic layer with the ammonium salt byproduct remaining in the aqueous layer.

In some embodiments, up to four equivalents of the secondary amine may be replaced by triethylamine or another suitable base. This variation may be particularly useful if the secondary ammonium salt byproduct is hard to separate.

Other suitable bases include tertiary amines and non-nucleophilic bases, including, but not limited to: carbonate salts, such as K ₂ C0 ₃ and CS2CO3; Ν,Ν-diwo-propylethylamine (DIPEA, also known as Hunig 's Base); and l,8-diazabicycloundec-7-ene (DBU). The triaminocyclopropenium chloride product may be isolated by crystallisation from

CH ₂ Cl ₂ /diethylether.

In some embodiments, the formation of secondary ammonium salt may be avoided by reacting tetrachlorocyclopropene with an aminosilane (R. Weiss and K. Schloter, Tetrahedron Lett. , 1975, 40, 3491, which is incorporated herein in its entirety by reference). The triaminocyclopropenium chloride may be purified by a number of techniques including:

(i) extracting the triaminocyclopropenium chloride from an aqueous solution using CH ₂ C1 ₂ or CHCI ₃ then removing the organic solvent;

(ii) adding a 1 :2 mixture of acetonitrile:toluene to the dried triaminocyclopropenium chloride and secondary ammonium chloride. The solution can be cooled to precipitate out the secondary ammonium chloride, which may be filtered off;

(iii) adding acetone to precipitate the secondary ammonium chloride, which may be filtered from the solution comprising the triaminocyclopropenium chloride; and

(iv) adding aqueous NaOH to convert the secondary ammonium chloride to the corresponding secondary amine which may removed by washing with petroleum ether or diethyl ether. In those embodiments wherein the secondary amine is volatile, extraction may be unnecessary. The aqueous solution comprising the triaminocyclopropenium chloride may be neutralized with HCl before removing water. Acetone may be added to precipitate NaCl, which may be filtered off. Alternatively, the NaCl may be removed by washing a chloroform or dichloromethane solution of the triaminocyclopropenium chloride with water. In some embodiments, a combination of any two or more of the methods (i)-(iv) may be used, depending on the absolute and relative solubility properties of the triaminocyclopropenium chloride, secondary ammonium chloride and secondary amine. Other purification methods may also be used, for example ion exchange chromatography and selective absorption using molecular sieves.

The triaminocyclopropenium chloride salts are also useful as intermediates in the preparation of other triaminocyclopropenium salts by anion metathesis. Anion metathesis can be carried out by a variety of standard techniques known to those persons skilled in the art. Such techniques include, but are not limited to:

(i) addition of an aqueous solution of a strong acid, for example H ₂ S0 ₄ , HBF ₄ , HBr, HN0 ₃ or HPF ₆ , followed by extraction with an organic solvent such as dichloromethane or diethylether;

(ii) addition of an aqueous solution of a group 1 metal or ammonium salt of a hydrophobic anion, for example LiCF ₃ S0 ₃ , followed by extraction with an organic solvent such as dichloromethane or diethylether;

(iii) addition of a silver salt, for example AgCF ₃ S0 ₃ , AgDCA, AgN0 ₃ or Ag[CBnHi ₂ ], to precipitate AgCl that can then be removed by filtration (this can be carried out in aqueous solution as well as in organic solvents such as methanol);

(iv) use of ion chromatography to exchange chloride for OFT followed by addition of a weak acid, for example CF ₃ COOH or HF;

(v) use of an ion-exchange resin containing pre-loaded anion, for example [CH ₂ =CHS0 ₃ ] ^" ;

(vi) exchange of halide ions, for example chloride, bromide or iodide, by reaction with alkylating agents, for example Me ₂ S0 ₄ , MeOTs, [Me ₃ 0]BF ₄ or [Et ₃ 0][PF ₆ ] (P. D. Vu, A. J. Boydston, C. W.

Bielawski, Green Chem. 2007, 9, 1158-9, which is incorporated herein in its entirety by reference); and

(vii) exchange of chloride for iodide by reaction with iodoethane.

A person skilled in the art can select the appropriate method, taking into account factors such as the relative solubility and miscibility properties of the reagents and products, the degree of purity required and the scale of the reaction. For example, water immiscible products are most easily prepared by methods (i) and (ii) whereas water miscible salts are generally better prepared using methods (iii), (iv) or (v). The use of silver salts provides products with low halide residues. Such products may, however, contain traces of silver.

Triaminocyclopropenium salts wherein two amino groups are the same (R ⁵ = R ¹ and R ⁶ = R ² or R ⁶ = R ⁵ = R = R ) can be synthesised by converting a triaminocyclopropenium salt wherein R = R = R = R = R = R ¹ , or wherein R ⁵ = R ³ = R ¹ and R ⁶ = R ⁴ = R ² , to the corresponding cyclopropenone, alkylating the cyclopropenone to a diaminoalkoxycyclopropemum salt, and reacting with a primary or secondary amine to give the desired product, as illustrated in Scheme 1. odide

HNR ³ R ⁴ Alkyl-OH

Scheme 1

The first step, in which the cyclopropenone is formed, also forms an amine which is typically removed prior to the alkylation, to prevent it being alkylated to an ammonium salt. The amine may be removed, for example, under reduced pressure or by washing with diethyl ether or another suitable non-polar solvent.

A number of alkylating agents are suitable for use in the alkylation step. In some embodiments, and as illustrated in Scheme 1 , the alkylating agent is an alkyl iodide. Advantageously, the use of alkyl iodides results in triaminocyclopropenium iodide salts that are suitable for conversion to the corresponding triaminocyclopropenium fluoride salts. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used. For example, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me ₃ 0]BF ₄ provides the tetrafluoroborate salt directly.

In some embodiments, wherein the alkylating agent is an alkyl iodide, the alkyl iodide is preferably methyl iodide or ethyl iodide. Advantageously, methyl iodide and ethyl iodide, and the corresponding alcohols formed during the alkylation (methanol and ethanol, respectively), are volatile and may be conveniently removed under reduced pressure. The invention also contemplates embodiments in which a triaminocyclopropenium salt having three different amino groups is prepared from a triaminocyclopropenium salt wherein two amino groups are the same, as illustrated in Scheme 2.

Scheme 2

A number of alkylating agents (RX) are suitable for use in the alkylation step. In some embodiments, the alkylating agent is an alkyl iodide. Advantageously, the use of alkyl iodides results in

triaminocyclopropenium iodide salts that are suitable for conversion to the corresponding

triaminocyclopropenium fluoride salts. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used, for example, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me ₃ 0]BF ₄ provides the tetrafluoroborate salt directly.

The invention also contemplates embodiments in which the product obtained following the alkylation step shown in Scheme 2 is reacted with a natural or non-natural alpha-amino acid, as illustrated in Scheme 3. Reaction of the initial product, in which R ⁵ is H and R ⁶ is -CH(R ^A )-C0 ₂ H, with 2 equivalents of butyllithium generates the anion [C ₃ (R ¹ R ² )(R ³ R ⁴ )=N(CH(R ^A )COO)] ^_ . Reaction of

[C ₃ (R'R ² )(R ³ R ⁴ )=N(CH(R ^A )COO)]- with an alkylating agent (R'X') provides a doubly alkylated product, in which R ⁵ is R' and R ⁶ is -CH(R ^A )-C0 ₂ R'. Those persons skilled in the art will appreciate that various other bases, including alkyl- and aryllithium reagents, for example, may be used instead of butyllithium to generate the anion.

Scheme 3

A number of alkylating agents ( 'X') are suitable for use in the alkylation step. In some embodiments, the alkylating agent is dimethylsulfate. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used, for example, alkyl iodides provide the iodide salt directly, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me ₃ 0]BF ₄ provides the tetrafluoroborate salt directly.

Advantageously, the doubly alkylated products are non-protic and would, therefore, be expected to have lower viscosities.

In some embodiments, the doubly alkylated product, in which R ⁵ is R' and R ⁶ is -CH(R ^A )-C0 ₂ R', in Scheme 3 is unstable to hydrolysis under acid and/or basic conditions. Accordingly, the invention also contemplates embodiments in which the product obtained following the alkylation step shown in Scheme 2 is reacted with a natural or non-natural alpha-amino acid, as illustrated in Scheme 4. In some of these embodiments, the product in which R ⁵ is H and R ⁶ is -CH(R ^A )-C0 ₂ H, may be isolated with significant amounts of the corresponding zwitterionic species in which R ⁵ is H and R ⁶ is -CH(R ^A )-C0 ₂ ^" . The amount of zwitterion formed generally increases with the hydrophilicity of the anion.

Scheme 4

The invention contemplates embodiments in which a triaminocyclopropenium salt wherein R ⁶ is alkyl is prepared from a protic triaminocyclopropenium salt, wherein R ⁶ is H, as illustrated in Scheme 5.

Scheme 5

The protic triaminocyclopropenium salt, wherein R ⁶ is H, is first reacted with a base, which in Scheme 5 is illustrated as butyllithium. Those persons skilled in the art will appreciate that various other bases, including other alkyl- and aryllithium reagents, sodium hydroxide and other bases, for example, may be used instead of butyllithium. A number of alkylating agents are suitable for use in the alkylation step. In some embodiments, the alkylating agent is dimethylsulfate. The use of dimethylsulfate results in triaminocyclopropenium methylsulfate salts, and the methylsulfate anion may be readily exchanged to form other salts. Other reactive alkylating reagents may also be used, for example, alkyl iodides provide the iodide salt directly, methyl trifluoromethanesulfonate provides the trifluoromethanesulfonate salt directly, and [Me ₃ 0]BF ₄ provides the tetrafluoroborate salt directly. Accordingly, in some embodiments, the present invention provides a method for preparing a compound of the invention substantially as herein described. In some embodiments, the present invention provides a method for preparing a compound of the invention substantially as herein described with reference to Scheme 1, Scheme 2, Scheme 3, Scheme 4, or Scheme 5. Triaminocyclopropenium salts comprising basic anions, for example carboxylates and fluoride, can be water sensitive. The formation of hydroxide can lead to cyclopropenone formation at elevated temperatures or with significant hydroxide ion concentration. Accordingly, in some embodiments, the triaminocyclopropenium salts are azeotrope dried in vacuo with benzene or ethanol, for example, at ambient temperature, and stored under anhydrous conditions. Other techniques may be used to dry the triaminocyclopropenium salts, for example: drying in vacuo at 70 °C; addition of ethanol or propanol and removal of the alcohol/water azeotrope in vacuo; and bubbling dry dinitrogen gas through the liquid triaminocyclopropenium salt.

Ionic liquids

The triaminocyclopropenium salts are suitable for use as ionic liquids. The term "ionic liquid", as used herein, means an organic salt or hydrate or solvate thereof that is in liquid form at or below about 100 °C.

Accordingly, in an eighth aspect, the present invention provides an ionic liquid comprising a

triaminocyclopropenium cation and an anion.

Some embodiments provide a compound comprising a triaminocyclopropenium cation and an anion, wherein the compound is in liquid form at or below about 100 °C.

In a ninth aspect, the present invention provides an ionic liquid comprising a compound of the invention.

In some embodiments, the ionic liquid consists essentially of a compound of the invention.

The anion (X ^q~ ) of the ionic liquid of the invention is any anion which, when associated with the selected triaminocyclopropenium cation, results in a salt that behaves as an ionic liquid. As is known in the art, the composition and structure of the cation and the anion may significantly affect the chemical and physical properties, for example melting point, volatility, stability, viscosity and hydrophobicity, of the resulting ionic liquid.

Compared to the ammonium, phosphonium, and guanidinium cations, triaminocyclopropenium cations have a greater dispersion of the positive charge (that is, reduced charge density) while compared to the imidazolium, pyridinium and triazonium cations, they have reduced hydrogen bond donor capabilities. Consequently, triaminocyclopropenium salts generally exhibit weak ion-pair interactions.

The strength of the ion-pair interaction can be further influenced by selecting weakly interacting anions, which generally have low charge density and moderate size.

The melting point is typically reduced in triaminocyclopropenium salts that have low symmetry in the cation and/or anion, and in salts in which the Ri-R.6 groups have higher conformational flexibility. For example, the melting point generally decreases in the alkyl series wherein Ri-R.6 are identical: methyl > ethyl > propyl > butyl. Similarly, the melting point for triaminocyclopropenium salts in which Ri-Re are w-propyl is generally lower than that for the corresponding salts in which R1-R6 are wo-propyl; and the melting point for triaminocyclopropenium salts in which R1-R6 are ethyl is generally lower than that for the corresponding salts of the cyclic analogue in which NRjR ₂ , NR ₃ R ₄ , and NR ₅ R ₂ are pyrrolidinyl.

Larger triaminocyclopropenium cations generally result in reduced ion-pair interactions and lower melting points. However, for particularly large cations, van der Waals interactions can become more significant as the cation size increases, resulting in increased melting points and viscosities.

Smaller Ri-Re groups and smaller anions tend to lower viscosities.

Protic substituents tend to increase melting points and viscosities via hydrogen bonding, whereas non- interacting substituents, such as alkyl and alkoxyalkyl (for example CH ₃ OCH ₂ -) groups, tend to lower melting points and viscosities. Aryl groups tend to increase melting points and viscosities due to ττ-τ stacking between aromatic rings. Accordingly, in some embodiments, the triaminocyclopropenium cation comprises a limited number of aryl groups, preferably three or fewer, more preferably two or fewer.

Fluorinated anions interact weakly with cations, which typically results in low melting points and low viscosities. Charge delocalisation on the cation and/or anion also reduces anion/cation interactions and typically results in lower melting points and viscosities.

The triaminocyclopropenium salts may be compared to analogous guanidinium salts, since both cations are stabilised by three electron-donating amino groups and have Z ⁾ _3h symmetry. melts at 41 °C whereas a melting point of 147 °C has been reported for the guanidinium analogue; [C(NBu ₂ )3]Cl.

In one embodiment, the ionic liquid comprises a compound selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate; (8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium -toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(Π) tris(dipropylamino)cyclopropenium chloride;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(18) tris(dibutylamino)cyclopropenium chloride;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(26) tris(diethanolamino)cyclopropenium fluoride;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride; - I l l -

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(69) tris(dipentylamino)cyclopropenium dicyanoamide;

(70) tris(dihexylamino)cyclopropenium chloride;

(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(76) bis(diwo-propylarnino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(77) bis(diz ^' io-propylamino)dibutylaminocyclopropenium dicyanoamide;

(79) bis(diethylamino)hexylannnocyclopropenium bis(trifluoromethanesulfonyl)amide;

(80) bis(diethylamino)aminocyclopropenium methylsulfate;

(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;

(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide;

(86) bis(diethylamino)dihexylaminocyclopropenium iodide;

(87) tris(dimethylamino)cyclopropenium dicyanoamide;

(88) tris(dimethylamino)cyclopropenium thiocyanate;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;

(91 ) tris(dihexylamino)cyclopropenium dibutylphosphate;

(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;

(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(97) bis(diethylamino)-5-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;

(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(99) tris(dibutylamino)cyclopropenium isocyanate;

( 100) tris(dibutylamino)cyclopropenium trichlorostannate;

(101 ) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;

(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;

( 105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(106) bis(diniethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (2), (4)-(13), (15)-(26), (29)-(39), (41), (42), (44), (45), (47), (48), (50), (51), (54), (56), (57), and (59)-(65).

In another embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79)-(101), (103), and (105)-(107).

In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of:

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium ⁾ -toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(1 1) tris(dipropylamino)cyclopropenium chloride;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(18) tris(dibutylamino)cyclopropenium chloride;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide; (22) tris(dibutylaraino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(26) tris(diethanolamino)cyclopropenium fluoride;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

^• (38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(51) bis(diethylamino)diethanolaminocyclopropenium fluoride;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(69) tris(dipentylamino)cyclopropenium dicyanoamide;

(70) tris(dihexylamino)cyclopropenium chloride; - -

(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (72) tris(dihexylamino)cyclopropeniura dicyanoamide;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(76) bis(di/50-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;

(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(80) bis(diethylamino)aminocyclopropenium methylsulfate;

(81) bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(83) bis(diethylamino)butylaminocyclopropenium tetrafluoroborate;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide;

(86) bis(diethylamino)dihexylaminocyclopropenium iodide;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;

(91 ) tris(dihexylamino)cyclopropenium dibutylphosphate;

(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;

(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;

(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(99) tris(dibutylamino)cyclopropenium isocyanate;

(100) tris(dibutylamino)cyclopropenium trichlorostannate;

(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;

(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;

(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (4)-(13), (15)-(26), (29)-(39), (41), (42), (44), (45), (47), (48), (50), (51), (54), (56), (57), and (59)-(64). In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79)-(88), (83)-(86), (89)-(101), (103), and (105)-(107). In another embodiment, the ionic liquid comprises a compound selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium -toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(11) tris(dipropylamino)cyclopropenium chloride;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(18) tris(dibutylamino)cyclopropenium chloride;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; (45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)aniide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium methylsulfate;

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(69) tris(dipentylamino)cyclopropenium dicyanoamide;

(70) tris(dihexylamino)cyclopropenium chloride;

(71) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide;

(74) tris(didecylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;

(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(82) trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide;

(86) bis(diethylamino)dihexylaminocyclopropenium iodide;

(87) tris(dimethylamino)cyclopropenium dicyanoamide;

(88) tris(dimethylamino)cyclopropenium thiocyanate;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;

(91) tris(dihexylamino)cyclopropenium dibutylphosphate;

(92) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(95) bis(diethylamino)-S-( 1 -carboxy-2-methylpropylamino)cyclopropenium methylsulfate; (96) bis(diethylamino)-5-(l -carboxy-2-methylpropylamino)cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;

(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(99) tris(dibutylamino)cyclopropenium isocyanate;

(100) tris(dibutylamino)cyclopropenium trichlorostannate;

(101 ) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;

(103) bis(diethylamino)dii50-propylaminocyclopropenium dicyanoamide;

(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

( 107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (2), (4)-(9), (1 1)-(13), (15)-(19), (21)-(25), (29)-(36), (38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(65).

In one embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (2), (4)-(13), (15)-(25), (29)-(38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(65).

In another embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (10), (20), (37), (68)-(72), (74)-(77), (79), (82), (84)-(101), (103), and (105)-(107).

In another embodiment, the ionic liquid comprises a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79), (82), (84)-(101 ), (103), and (105)-(107).

In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of:

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium /?-toluenesulfonate;

(10) tris(diethylamino)cyclopropenium trifluoromethanesulfonate;

(11) tris(dipropylamino)cyclopropenium chloride;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide; (15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(18) tris(dibutylamino)cyclopropenium chloride;

(19) tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(20) tris(dibutylamino)cyclopropenium bromide;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(37) tris(octadecylmethylamino)cyclopropenium chloride;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(44) bis(diethylamino)dibutylannnocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide; (64) bis(diethylamino)-S-( 1 -carboxylethylamino)cyclopropenium methylsulfate;

(68) tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(69) tris(dipentylamino)cyclopropenium dicyanoamide;

(70) tris(dihexylamino)cyclopropenium chloride;

(71 ) tris(dihexylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(72) tris(dihexylamino)cyclopropenium dicyanoamide;

(74) tris(didecylarnino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(75) tris(didecylamino)cyclopropenium dicyanoamide;

(76) bis(diwo-propylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(77) bis(diwo-propylamino)dibutylaminocyclopropenium dicyanoamide;

(79) bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(84) bis(diethylamino)dibutylaminocyclopropenium iodide;

(85) tris(diethylamino)cyclopropenium iodide;

(86) bis(diethylamino)dihexylaminocyclopropenium iodide;

(89) tris(dibutylamino)cyclopropenium tetracyanoborate;

(90) tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate;

(91) tris(dihexylamino)cyclopropenium dibutylphosphate;

(92) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(93) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate;

(94) bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(95) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium methylsulfate;

(96) bis(diethylamino)-S-(l -carboxy-2-methylpropylamino)cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(97) bis(diethylamino)-S-( 1 -carboxy-2-hydroxylpropylamino)cyclopropenium methylsulfate;

(98) bis(diethylamino)-S-(l -carboxy-2-hydroxylpropylamino))cyclopropenium

bis(trifluoromethanesulfonyl)amide;

(99) tris(dibutylamino)cyclopropenium isocyanate;

(100) tris(dibutylamino)cyclopropenium trichlorostannate;

(101) bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate;

(103) bis(diethylamino)diwo-propylaminocyclopropenium dicyanoamide;

(105) bis(dimethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(106) bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide; and

(107) bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide.

In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (4)-(9), (1 1)-(13), (15)-(19), (21)-(25), (29)-(36), (38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(64). In one embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (4)-(13), (15)-(25), (29)-(38), (39), (41), (42), (44), (45), (47), (48), (50), (54), (56), (57), and (59)-(64).

In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (10), (20), (37), (68)-(72), (74)-(77), (79), (84)-(86), (89)-(101), (103), and (105)-(107).

In another embodiment, the ionic liquid consists essentially of a compound selected from the group consisting of compounds (68)-(72), (74)-(77), (79), (84)-(86), (89)-(101), (103), and (105)-(107).

In another embodiment, the ionic liquid comprises a compound selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium -toluenesulfonate;

(12) tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(13) tris(dipropylamino)cyclopropenium dicyanoamide;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(21) tris(dibutylamino)cyclopropenium dicyanoamide;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide; (39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(56) bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l-carboxylethylamino)cyclopropenium methylsulfate; and

(65) bis(diz o-propylamino)dibutylaminocyclopropenium chloride.

In another preferred embodiment, the ionic liquid comprises a compound selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium/?-toluenesulfonate;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(22) tris(dibutylamino)cyclopropenium nitrate;

(23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide; (31) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)arnide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(38) tris(octadecylmethylannno)cyclopropenium bis(trifluorornethanesulfonyl)amide;

(39) tris(octadecylraethylamino)cyclopropenium dicyanoamide;

(41) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; and

(65) bis(diwo-propylamino)dibutylaminocyclopropenium chloride.

In another embodiment, the ionic liquid comprises a compound selected from the group consisting of:

(2) tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(4) tris(diethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(5) tris(diethylamino)cyclopropenium dicyanoamide;

(6) tris(diethylamino)cyclopropenium nitrate;

(7) tris(diethylamino)cyclopropenium tetrafluoroborate;

(8) tris(diethylamino)cyclopropenium thiocyanate;

(9) tris(diethylamino)cyclopropenium /?-toluenesulfonate;

(15) tris(dipropylamino)cyclopropenium fluoride ethanol;

(16) tris(dipropylamino)cyclopropenium nitrate;

(17) tris(dipropylamino)cyclopropenium tetrafluoroborate;

(22) tris(dibutylamino)cyclopropenium nitrate; (23) tris(dibutylamino)cyclopropenium tetrafluoroborate;

(24) tris(dibutylamino)cyclopropenium trifluoromethanesulfonate;

(25) tris(diethanolamino)cyclopropenium chloride;

(29) tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(30) tris(diallylamino)cyclopropenium dicyanoamide;

(31 ) tris(butylmethylamino)cyclopropenium chloride;

(32) tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(33) tris(butylmethylamino)cyclopropenium dicyanoamide;

(34) tris(butylmethylamino)cyclopropenium nitrate;

(35) tris(butylmethylamino)cyclopropenium tetrafluoroborate;

(36) tris(butylmethylamino)cyclopropenium thiocyanate;

(38) tris(octadecylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide;

(39) tris(octadecylmethylamino)cyclopropenium dicyanoamide;

(41 ) bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(42) bis(diethylamino)dimethylaminocyclopropenium dicyanoamide;

(44) bis(diethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(45) bis(diethylamino)dibutylaminocyclopropenium dicyanoamide;

(47) bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(48) bis(diethylamino)dihexylaminocyclopropenium dicyanoamide;

(50) bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(54) bis(diethylamino)diallylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(57) bis(diethylamino)butylmethylaminocyclopropenium dicyanoamide;

(59) bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(60) bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide;

(61) bis(diethylamino)butylaminocyclopropenium methylsulfate;

(62) bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide;

(63) bis(diethylamino)butylaminocyclopropenium dicyanoamide;

(64) bis(diethylamino)-S-(l -carboxylethylamino)cyclopropenium methylsulfate; and

(65) bis(diz.yo-propylamino)dibutylaminocyclopropenium chloride. In some embodiments, the ionic liquid comprises a compound selected from any of the compounds identified in the embodiments of the first to the seventh aspects of the invention disclosed above.

The ionic liquid of the invention is in liquid form at or below about 100 °C. In some embodiments, the ionic liquid is in liquid form at or below about 50 °C. In some embodiments, the ionic liquid is in liquid form at or below room temperature, for example in liquid form at or less than about 15, 20, 25, or 30 °C. In other embodiments, the ionic liquid is in liquid form at or below about 0 °C, -5 °C, -10 °C, -20 °C, or -30 °C. The invention also contemplates ionic liquids that are solid or semi-solid at about room temperature or above, but which can be melted at a higher temperature.

The conductivity of the ionic liquid of the invention is preferably at least 0.01 mS/cm at a temperature between about 20 °C and about 100 °C. In some embodiments, the conductivity of the ionic liquid is at least Ο.Οί, 0.05, 0.1, 0.5, 1, 5, or 10.

Viscosity is typically an important property of ionic liquids as lower viscosities lead to higher conductivities as well as greater ease of processibility. However, higher viscosities may be useful in some embodiments, for example those embodiments wherein the ionic liquid is for use in or as a lubricant. The viscosity of the ionic liquid of the invention is preferably less than 50,000 mPa.s at a temperature between about 20 °C and about 100 °C. In some embodiments, the viscosity of the ionic liquid is less than about 25,000 mPa.s, 10,000 mPa.s, 5,000 mPa.s, 2,000 mPa.s, 1,000 mPa.s, 800 mPa.s, or 700 mPa.s, 600 mPa.s, 500 mPa.s, 400 mPa.s, 300 mPa.s, 200 mPa.s, 100 mPa.s, 50 mPa.s, or 25 mPa.s.

The ionic liquid of the invention can be of any suitable purity level. In some embodiments, the ionic liquid has a purity at least about 95%, 96%, 97%, 98%, 99%, 99.5%, or 99.9% by weight. In some embodiments, the ionic liquid is substantially free of salt byproducts (for example, secondary ammonium salts) that may be produced during synthesis of the triaminocyclopropenium salt. In some embodiments, the ionic liquid contains less than about 1% by weight of salt byproducts, preferably less than about 0.5%, 0.1%, 0.01%, or even 0.001% by weight of salt byproducts. The ionic liquids of the invention may be used as solvents, for example as reaction media or for extractions.

In some embodiments, the ionic liquid comprises a chiral triaminocyclopropenium cation and is useful as a solvent for synthesis.

Accordingly, in a tenth aspect, the present invention provides use of a compound of the invention as a solvent. The invention also provides a compound of the invention that is in liquid form at or below about 100 °C for use as a solvent.

The ionic liquids of the invention may be used as electrolytes, for example in batteries, capacitors, and electrochemical cells.

Accordingly, in an eleventh aspect, the present invention provides use of a compound of the invention as an electrolyte. The invention also provides a compound of the invention that is in liquid form at or below about 100 °C for use as an electrolyte. In some embodiments, the ionic liquids of the invention may be mixed with other ionic liquids and/or other additives.

For example, the invention contemplates embodiments in which dimethylformamide and/or

dimethylsulfoxide are used as additives to aid the dissolution of cellulose in the ionic liquid. In some embodiments, the ionic liquids of the invention comprise fluoride anions. Accordingly, in some embodiments, the present invention provides an ionic liquid comprising a triaminocyclopropenium cation as defined for any of the embodiments of the first to the sixth aspects of the invention disclosed above and a fluoride anion. In some embodiments, the present invention provides an ionic liquid consisting essentially of a triaminocyclopropenium cation as defined for any of the embodiments of the first to the sixth aspects of the invention disclosed above and a fluoride anion.

While many organic fluoride salts are known, these materials are generally thermally unstable when pure due to the high basicity of the "naked" fluoride anion. [Bu ₄ N]F, for example, is only available commercially as a hydrate, in tetrahydrofuran or water solution, or supported on silica gel or alumina. Organic fluoride salts are also typically not stable as liquids, and decompose before melting. Common ionic liquid cations, such as ammonium, phosphonium, pyridinium and imidazolium, are all well-known to decompose with fluoride because they have acidic hydrogen atoms on the carbon atoms alpha to nitrogen or phosphorus. In comparison, the triaminocyclopropenium cation has low acidity because there are no aromatic C-H groups and the charge is delocalised over three nitrogen and three carbon atoms.

In some preferred embodiments, the triaminocyclopropenium cation in the ionic liquid fluorides of the invention comprises at least one hydroxyl or amino functional group. In some preferred embodiments, the triaminocyclopropenium cation in the ionic liquid fluorides of the invention comprises at least one hydroxyl functional group. In some embodiments, at least one of Ri-Re is Ci_6 alkyl-OH, Ci.e alkyl-NH ₂ or Ci-6 alkyl-NH-Ci_6 alkyl. In some embodiments, at least one of Ri-Re is Ci_ ₆ alkyl-OH. In some embodiments, at least one of Ri-R.6 is -CH2CH2OH or -CH2CH2NH2. In some embodiments, at least one of R1-R6 is -CH2CH2OH. The hydroxyl or amino functional group reduces the basicity of the fluoride anion when it is associated with the triaminocyclopropenium cation.

In some embodiments, when used as ionic liquids, the compounds of the invention are unsolvated and, in particular, unhydrated.

In some embodiments, the ionic liquids of the invention comprise solvated triaminocyclopropenium salts. In some embodiments, solvation may increase the stability of the triaminocyclopropenium salt.

Advantageously, moderate proton donor solvates reduce the nucleophilicity and basicity of the fluoride anion, which hinders decomposition routes. In some embodiments, the solvate comprises an alcohol, or primary or secondary amine. In some embodiments, the solvate comprises methanol, ethanol, propanol, wo-propanol, H-butanol, wo-butanol, sec-butanol, tert-butanol, ethylamine, monoethanolamine, or diethanolamine. In some embodiments, the solvate comprises ethanol.

In a twelfth aspect, the present invention provides use of a compound of the invention for gas storage. The invention also provides a compound of the invention that is in liquid form at or below about 100 °C for use in gas storage.

In some embodiments, the stored gas is a weak to moderate proton donor. Such gases include NH ₃ , MeNH ₂ , H ₂ S, CH and C ₂ H ₆ .

The fluoride-containing ionic liquids of the invention are particularly suitable for use as electrolytes. The invention also contemplates their application in pharmaceutical synthesis and for gas storage applications. The application of the fluoride-containing ionic liquids of the invention for hydrogen storage, in particular, is also contemplated.

The following non-limiting examples are provided to illustrate the present invention and in no way limit the scope thereof.

EXAMPLES

Abbreviations

Bu -(CH ₂ ) ₃ CH ₃

DCA dicyanoamide

Dec -(CH ₂ ) ₉ CH ₃

DSC differential scanning calorimetry

Et -CH ₂ CH ₃

EI electron impact ionisation

ES electrospray ionisation

FAP tris(pentafluoroethyl)trifluorophosphate

Hex -(CH ₂ ) ₅ CH ₃

Me -CH ₃

MS mass spectrometry

NMR nuclear magnetic resonance

OTf trifiuoromethanesulfonate

Pent -(CH ₂ ) ₄ CH ₃

Ph phenyl

Pr -(CH ₂ ) ₂ CH ₃

i-Pr -CH(CH ₃ ) ₂

St -(CH ₂ ) ₁₇ CH ₃ TFSA bis(trifluoromethanesulfonyl)amide

TGA thermogravimetric analysis

General procedures

All reagents and solvents were obtained from commercial sources. Liquid reagents and solvents were typically distilled under a dinitrogen atmosphere prior to use.

All operations were performed using standard Schlenk techniques with a dinitrogen atmosphere in order to reduce exposure to water.

Ή- and ¹³ C {'H} -NMR spectra were collected on a Varian Unity-300 operating at 300 and 75 MHz respectively, or on a Varian INOVA-500 operating at 500 and 126 MHz respectively, in CDC1 ₃ , referenced to residual solvent peaks unless otherwise indicated.

DSC was performed on a Perkin Elmer Q100. Samples of mass 5-20 mg were sealed in a vented aluminium pan and placed in the furnace with a 50 mL/min nitrogen stream; the temperature was raised at

10 °C/min.

Viscosities were measured on an Anton Parr AMVn falling-ball viscometer or a Brookfield- Wells cone- and-plate viscometer operating at 0.005 - 0.2 s ^_1 rotation speed range.

TGA data were collected on dried samples using a TA Instruments SDT Q600 at 10 °C/min after further drying at 100 °C for one hour in the instrument.

AC Impedance Spectroscopy was performed on a Hewlett Packard 4284A precision LCR meter, with a range of 20 Hz to 1 MHz. Samples were tested in a cylindrical cell with a "gun barrel" design, where 6 sample wells surround a heating element in the centre. Measurements were calibrated using a 0.001 M

KC1 standard solution. Samples were prepared for analysis by melting into a sample well. While samples were molten, a counter electrode was plunged into the sample, with a Teflon sleeve around the counter electrode making a seal. Measurements were run in a copper Faraday cage, using liquid nitrogen to cool the cell and vermiculite to insulate the cell. Electrospray mass spectrometry was carried out on a Micromass LCT, with samples dissolved in acetonitrile.

Water contents were determined by Karl Fischer titration using a Metrohm 831 KF coulometer.

Chloride contents were determined using a AutolabEco Chemie, with associated GPES software, under a dinitrogen atmosphere. The electrodes were either a glassy carbon (3 mm diameter) or platinum (1 mm diameter) working electrode, a platinum wire counter electrode and a silver reference electrode. Microanalysis was performed by the Campbell Microanalytical Laboratory, Department of Chemistry, University of Otago, Dunedin, New Zealand.

Trisanilmocyclopropenium chloride ([C ₃ (NPhH) ₃ ]Cl) was prepared according to the procedure described in Weiss, R.; Hertel, M. J. Chem. Soc, Chem. Comm. 1980, 223-4, which is incorporated herein in its entirety by reference.

Bis(dimethylamino)cyclopropenone was prepared by the route described in Wilcox, C; Bresloti, R. Tetrahedron Lett. 1980, 21, 3241-2, which is incorporated herein in its entirety by reference.

Preparation of triaminocyclopropenium chloride salts from pentachlorocyclopropane

Pentachlorocyclopropane was added to freshly distilled CH2CI2 (from CaH ₂ ). This was stirred at 0 °C under a dinitrogen atmosphere. A 7-8 fold excess of amine was added over 1 h and the solution stirred at 0 °C for a further 4 h and then at ambient temperature for 18 h, before heating to reflux (65 °C) for 5 h. The solution, usually yellow/orange in colour, was then placed under vacuum to remove the solvent.

The order of addition of pentachlorocyclopropane and amine can be reversed and, in some reactions, this resulted in products that were less coloured. In some reactions, four equivalents of the secondary amine was replaced by triethylamine. This modification may be useful if the secondary ammonium salt byproduct is hard to separate.

Removal of the secondary ammonium salts was carried out in several ways. Four options are outlined below. For some reactions, it was advantageous to use a combination of methods, which were selected depending on the solubilities of the species involved. (i) The triaminocyclopropenium salt was extracted from an aqueous solution using chloroform or dichloromethane. The organic solvent was removed under vacuum.

(ii) A 1 :2 mixture of acetonitrile:toluene was added to the dried triaminocyclopropenium and secondary ammonium salts. The solution was cooled in the freezer to precipitate out the secondary ammonium salt, which was then filtered off. (iii) Dichloromethane was removed in vacuo. Acetone was added to precipitate the secondary ammonium salt, which was then filtered from the solution comprising the triaminocyclopropenium salt.

(iv) Dichloromethane was removed in vacuo. Aqueous NaOH was added to convert the secondary ammonium salt to the amine which was then removed by washing with petroleum ether or diethyl ether. The aqueous solution was then neutralized with HC1 before removing the water in vacuo. Addition of acetone precipitated NaCl, which was filtered off. NaCl could also be removed by washing a chloroform or dichloromethane solution of the triaminocyclopropenium salt with water. Preparation of methylsulfate triaminocyclopropenium salts from cyclopropenone

Various triaminocyclopropenium methylsulfate salts were prepared from the respective

diaminocyclopropenone. The cyclopropenone was dried, typically by using an wo-propanol or ethanol azetrope. Dimethylsulfate was added while under a dry, inert atmosphere, and the solution was then stirred for approximately 1 h. An excess of a primary or secondary amine was then added, and the mixture was stirred for a further 1 h. Excess amine was removed by washing with diethylether or petroleum ether and ammonium salts were removed by water-chloroform extractions.

(1) Tris(dimethylamino)cycIopropenium chloride, [C ₃ (NMe ₂ )3]Cl

C3CI5H (3.53 g, 16.5 mmol) and HNMe ₂ (10.2 g, 226 mmol) gave an orange solid (1.81 g, 54% yield) after separation from dimethylammonium chloride using option (ii) twice. Ή NMR (500 MHz, CDC1 ₃ ): δ 3.16 (s, NCH3). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 116.76 (C ₃ ), 42.11 (N H ₃ ). ES-MS ⁺ : m/z 168 (100%, M ⁺ ).

(2) Tris(dimethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NMe ₂ ) ₃ ]TFSA [C ₃ (NMe ₂ ) ₃ ]Cl (3.5 g, 17.2 mmol) was stirred with LiTFSA (15.0 g, 52.3 mmol) in H ₂ 0 (200 mL). The product was extracted with dichloromethane:diethyl ether (1:3, 200 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield colourless crystals (1.5 g, 19.5%). Ή, ¹³ C NMR and MS ⁺ as for

[C ₃ (NMe ₂ )3]Cl with an additional peak at 119.8 ppm in the ^I3 C NMR spectrum due to TFSA.

(3) Tris(diethylamino)cyclopropenium chloride, [C3(NEt ₂ ) ₃ ]Cl C3CI5H (66.7g, 311 mmol) and HNEt ₂ (213 g, 2910 mmol) gave an orange liquid (77.0 g, 86.0% yield), that slowly solidified after separation from diethylammonium chloride using options (iii), (iv) and then (i). Ή NMR (CDCI3, 300 MHz): 8 3.36 (q, ³ J _HH = 7.3 Hz, 12H, NC¾), 1.22 (t, ³ J _HH = 7.4 Hz, 18H, NCH ₂ C¾). ¹³ C NMR (CDCI ₃ , 75 MHz): b 115.99 (C ₃ ), 47.07 (CH ₂ ), 14.24 (CH ₃ ). ES-MS ⁺ : m/z 252 (100%, M ⁺ ). (4) Tris(diethylamino)cyclopropenium bis(trifluoromethanesuIfonyl)amide, [C ₃ (NEt ₂ ) ₃ ]TFSA

[C ₃ (NEt ₂ ) ₃ ]Cl (7.30 g, 25.4 mmol) was stirred with LiTFSA (21.8 g, 76.0 mmol) in H ₂ 0 (200 mL). The product was extracted with chloroform (200 mL), washed with H ₂ 0 (3 x 200 mL) and dried in vacuo to yield an orange liquid (11.5 g, 85.2%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₃ ]Cl with an additional peak at 119.8 ppm in the ¹³ C NMR spectrum due to TFSA. (5) Tris(diethylamino)cyclopropenium dicyanoamide, [C3(NEt ₂ ) ₃ ]DCA

[[C ₃ (NEt ₂ ) ₃ ]Cl (8.30 g, 28.3 mmol) was stirred with NaDCA (9.50 g, 107 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (3x 100 mL) and dried in vacuo to yield an orange liquid (7.88 g, 85.8%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₃ ]Cl. (6) Tris(diethylamino)cyclopropenium nitrate, [C ₃ (NEt ₂ )3]N0 ₃

[C ₃ (NEt ₂ ) ₃ ]Cl (4.74 g, 16.5 mmol) was stirred with HN0 ₃ (5 mL, 69%, 77 mmol) in H ₂ 0 (50 mL). The product was extracted with dichloromethane (50 mL), washed with HN0 ₃ (5 mL, 69%, 77 mmol), washed with H ₂ 0 (3 x 50 mL) until the pH was neutral, and then dried in vacuo to yield an orange liquid (4.13 g, 79.6%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₃ ]Cl. (7) Tris(diethylamino)cyclopropenium tetrafluoroborate, [C ₃ (NEt ₂ )3]BF ₄

[C ₃ (NEt ₂ ) ₃ ]Cl (5.77 g, 20.1 mmol) was stirred with aqueous HBF ₄ (11 mL, 35%, 60 mmol) in H ₂ 0 (50 mL). The product was extracted with dichloromethane (50 mL) and washed again with aqueous HBF ₄ (1 1 mL, 35%, 60 mmol). The product was then washed with H ₂ 0 (3 x 50 mL), until the pH was neutral, and dried in vacuo, yielding an orange liquid (5.3 g, 78.4%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₃ ]Cl. (8) Tris(diethylamino)cyclopropenium thiocyanate, [C ₃ (NEt ₂ )3]SCN

[C ₃ (NEt ₂ ) ₃ ]Cl (5.03 g, 17.5 mmol) was stirred with NaSCN (1.43 g, 17.6 mmol) in H ₂ 0 (20 mL). The product was extracted with dichloromethane (10 mL) and the solvent removed in vacuo. This product was washed twice with NaSCN (1.43 g, 17.6 mmol) in H ₂ 0 (20 mL), then with H ₂ 0 (3 x 20 mL), and then dried in vacuo to yield a dark orange liquid (4.05 g, 74.7%). 'H, ¹³ C NMR and MS ⁺ as for

[C ₃ (NEt ₂ ) ₃ ]Cl.

(9) Tris(diethylamino)cycIopropenium 7-toluenesuIfonate, [C ₃ (NEt ₂ ) ₃ ] Jp-MeC ₆ H ₄ S0 ₃ ]

[C3(NEt ₂ ) ₃ ]Cl (4.99 g, 17.3 mmol) was stirred with para-toluenesulfonic acid (29.88 g, 173 mmol) in H ₂ 0 (200 mL). The product was extracted with chloroform (100 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield an orange liquid (6.59 g, 90.0%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₃ ]Cl. Additional peaks due to anion: Ή NMR (500 MHz, CDC1 ₃ ): δ 7.70 (d, ³ J _HH = 1.5 Hz, 2H, CH), 6.98 (d, ³ J _HH = 8.5 Hz, 2H, CH), 2.20 (s, 3H, C ₆ H ₄ CH ₃ ). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 144.46 (CS0 ₃ ), 137.38 (CH), 127.39 (CH), 125.52 (CCH ₃ ).

(10) Tris(diethylamino)cyclopropenium trifluoromethanesulfonate, [C ₃ (NEt ₂ )3]OTf

[C ₃ (NEt ₂ ) ₃ ]Cl (3.58 g, 12.5 mmol) was stirred with LiOTf (5.83 g, 37.4 mmol) in H ₂ 0 (200 mL). The product was extracted with dichloromethane (100 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield a yellow solid (4.51 g, 90.2%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₃ ]Cl. Additional peaks due to anion: ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 120.39 (q, J _CT = 322 Hz, CF ₃ ).

(11) Tris(diprop lamino)cyclopropenium chloride, [C ₃ (NPr ₂ ) ₃ ]Cl

HNPr ₂ (88.6 g, 0.875 mol) was dissolved in CH ₂ C1 ₂ (250 mL) and cooled to 0 °C. C ₃ C1 ₅ H (25.0 g, 0.117 mol) was added dropwise and the solution stirred overnight. The solution was refluxed for 3 h, before CH2CI2 and excess amine were removed in vacuo. Acetone (200 mL) was added and the [H ₂ NPr ₂ ]Cl precipitate was filtered off. After removal of acetone under vacuum, the residual [H ₂ NPr ₂ ]Cl was removed by washing a CH ₂ C1 ₂ solution (250 mL) with H ₂ 0 (3 x 150 mL). Removal of CH ₂ C1 ₂ in vacuo yielded an orange liquid, which solidified overnight (36.9 g, 84.9%). Ή NMR (500 MHz, CDC1 ₃ ): b 3.25 (t, ³ J _HH = 8.0 Hz, 12H, NCH ₂ ), 1.65 (m, 12Η, NCH ₂ CH ₂ ), 0.92 (t, ³ J _HH = 7.3 Hz, 18H, NCH ₂ CH ₂ CH ₃ ). ^I3 C NMR (126 MHz, CDC1 ₃ ): 8 1 15.98 (C ₃ ), 52.22 (NCH ₂ ), 21.81 (NCH ₂ H ₂ ), 10.52 (CH ₃ ). ES-MS ⁺ : m/z 336 (100%, M ⁺ ).

(12) Tris(dipropylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide, [C ₃ (NPr ₂ ) ₃ ]TFSA

Metathesis to the TFSA salt was carried out by mixing [C ₃ (NPr ₂ ) ₃ ]Cl (17.5 g, 47.1 mmol) with 3 equivalents of LiTFSA in H ₂ 0 (100 mL), followed by addition of CHC1 ₃ (100 mL) and washing with H ₂ 0 (3 x 100 mL). Removal of CHC1 ₃ in vacuo yielded an orange liquid (24 g, 83%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NPr ₂ ) ₃ ]Cl with an additional peak in the ¹³ C NMR due to TFSA. Water content: 100 ppm.

(13) Tris(dipropylamino)cyclopropenium dicyanoamide, [C ₃ (NPr ₂ )3]DCA

[C ₃ (NPr ₂ ) ₃ ]Cl (7.69 g, 20.7 mmol) was stirred with aqueous NaDCA (3.73 g, 41.9 mmol) in water (100 mL). The product was extracted with dichloromethane (50 mL) and washed with H ₂ 0 (3 x 100 mL).

Additional aqueous NaDCA (1.85 g, 20.8 mmol) was added and the organic layer was then washed with H ₂ 0 (4 x 100 mL) and dried in vacuo to yield a yellow liquid (11.5 g, 85.2%), which slowly crystallised. Ή, ^,3 C NMR and MS ⁺ as for [C ₃ (NPr ₂ ) ₃ ]Cl with an additional peak in the ¹³ C NMR due to DC A.

(14) Tris(dipropylamino)cyclopropenium fluoride diethanol, [C3(NPr ₂ ) ₃ ]F.2EtOH [C ₃ (NPr ₂ ) ₃ ]Cl (10.6 g, 28.5 mmol) was stirred in H ₂ 0 (450 mL), in a blacked-out flask, to which Ag ₂ 0 (6.7 g, 28.9 mmol) was added and stirring continued for 3 h. AgCl formed and was removed by filtering through Celite, before the solution was neutralized to pH 7.1 with aqueous HF. The solution was reduced in volume to 100 mL in vacuo, with drying being completed with ethanol azetrope drying (3 x 500 mL) to yield an orange liquid (12.4 g, 97.1 %). 2200 ppm H ₂ 0. A fluoride selective electrode showed 44300 ppm fluoride. Ή NMR (300 MHz, CDC1 ₃ ): δ 3.68 (q, J _HH = 7.03 Hz, 4H, CH ₃ CH ₂ OH), 3.27 (t, J _HH = 7.91 Hz, 12H, NG¾), 1.67 (m, 12H, NCH ₂ CH ₂ ), 1.21 (t, ³ J _HH = 7.03 Hz, 6H, CH ₃ CH ₂ OH), 0.94 (t, J _HH = 7.33 Hz, 18H, NCH ₂ CH ₂ CH ₃ ). ¹⁹ F NMR (282 MHz, D ₂ 0, C ₆ H ₅ F reference): δ 122.03 (s). (15) Tris(dipropylamino)cyclopropenium fluoride ethanol, [C ₃ (NPr ₂ ) ₃ ]F.EtOH

To remove one EtOH solvated molecule from [C ₃ (NPr ₂ ) ₃ ]F.2EtOH (2.5 g, 5.6 mmol), a benzene azetrope was used (20 mL, then 10 mL). This yielded a brown liquid (2.02 g, 90.4%). Ή NMR (300 MHz, CDC1 ₃ ): δ 3.67 (q, ³ J _HH = 7.03 Hz, 2H, CH ₃ CH ₂ OH), 3.26 (t, ³ J _HH = 7.91 Hz, 12H, NCH ₂ CH ₂ CH ₃ ), 1.66 (m, 12H, NCH ₂ CH ₂ CH ₃ ), 1.20 (t, ³ J _HH = 7.03 Hz, 3H, CHjCH ₂ OH), 0.93 (t, V _HH = 7.33 Hz, 18H,

NCH ₂ CH ₂ CH5). ¹³ C NMR and MS ⁺ as for cation of [C ₃ (NPr ₂ ) ₃ ]Cl. ¹⁹ F NMR as for [C ₃ (NPr ₂ ) ₃ ]F.2EtOH.

(16) Tris(dipropylamino)cyclopropenium nitrate, [C ₃ (NPr ₂ ) ₃ ]N0 ₃

[C ₃ (NPr ₂ ) ₃ ]Cl (7.49 g, 20.1 mmol) was dissolved in 20 mL of water. HNO ₃ (> 90%, 5.0 mL) was added to the solution, stirred and the [C ₃ (NPr ₂ )3]N0 ₃ was extracted with chloroform. HN0 ₃ (> 90%, 5.0 mL) was added to the chloroform extract, stirred and washed with 20 mL of water. The previous step was repeated. The resulting solution was washed with water until the pH was neutral. The solvent was removed under vacuum and the product formed an orange-brown solid (7.70 g, 96%). Ή, ^I3 C NMR and MS ⁺ as for [C ₃ (NPr ₂ ) ₃ ]Cl.

(17) Tris(dipropylamino)cyclopropenium tetrafluoroborate, [C ₃ (NPr ₂ ) ₃ ]BF ₄ [C ₃ (NPr ₂ ) ₃ ]Cl (7.49 g, 20.1 mmol) was dissolved in water (20 mL). HBF ₄ (35%, 10 mL) was added to the solution, stirred and the [C ₃ (NPr ₂ ) ₃ ]BF ₄ was then extracted with chloroform. HBF ₄ (35%, 10 mL) was added to the chloroform extract, stirred and washed with 20 mL of water. The previous step was repeated. The resulting solution was washed with water until the pH was neutral. The solvent was removed under vacuum and the product formed a white solid (7.96 g, 93%). Ή, ¹ C NMR and MS ⁺ as for [C ₃ (NPr ₂ ) ₃ ]Cl.

(18) Tris(dibutylamino)cycIopropenium chloride, [C ₃ (NBu ₂ ) ₃ ]Cl

C ₃ C1 ₅ H (25.0g, 1 17 mmol) and HNBu ₂ (123 g, 950 mmol) gave a light brown liquid (50.8 g, 95.5% yield) that slowly solidified. The product was separated from dibutylammonium chloride using option (iii) and then (i) with dichloromethane. This was followed by washing with petroleum ether (4 x 50 mL) to remove residual amine. Ή NMR (300 MHz, CDC1 ₃ ): δ 3.27 (t, ³ J _HH = 7.91 Hz, 12H, NCH ₂ ), 1.57 (m,

12H, NCH ₂ G¾), 1.29 (m, 12H, NCH ₂ CH ₂ CH ₂ ), 0.91 (t, ³ J _HH = 7.03 Hz, 18H, CH ₃ ). ^,3 C NMR (75MHz, CDCI ₃ ): δ 116.2 (C ₃ ), 52.6 (N H ₂ ), 30.7 (NCH ₂ H ₂ ), 19.6 (NCH ₂ CH ₂ CH ₂ ), 13.5 (CH ₃ ). ES-MS ⁺ : m/z 420 (100%, M ⁺ ).

(19) Tris(dibutylamino)cyclopropenium bis(trifluoromethanesulfonyI)amide, [C ₃ (NBu ₂ ) ₃ lTFSA [C ₃ (NBu ₂ ) ₃ ]Cl (10.74 g, 23.6 mmol) was stirred with aqueous LiTFSA (7.8 g, 27.2 mmol) in water (100 mL). The product was extracted with dichloromethane (40 mL) and washed with H ₂ 0 (2 x 40 mL). Additional aqueous LiTFSA (7.7 g, 26.8 mmol) was added, and the solution was then washed with H ₂ 0 (3 x 30 mL) and dried in vacuo to yield an orange liquid (12.9 g, 78.0%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl with an additional peak in the ¹³ C NMR due to TFSA.

(20) Tris(dibutylamino)cyclopropenium bromide, [C ₃ (NBu ₂ ) ₃ ]Br [C ₃ (NBu ₂ ) ₃ ]Cl (0.86 g, 1.9 mmol) was stirred with HBr (20 mL, 38%, 140 mmol). The product was extracted with chloroform (20 mL) and washed again with HBr (20 mL, 38%, 140 mmol). It was then washed with H ₂ 0 (3 x 20 mL) until the pH was neutral and dried in vacuo to yield a dark brown solid (0.5 g, 52%). Ή, ^l3 C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl.

(21) Tris(dibutylamino)cyclopropenium dicyanoamide, [C ₃ (NBu ₂ ) ₃ ]DCA [C ₃ (NBu ₂ ) ₃ ]Cl (6.00 g, 13.2 mmol) was stirred with AgDCA (7.8 g, 27.2 mmol) in H ₂ 0 (100 mL).

Dichloromethane (150 mL) was added to form a separate layer containing the traiminocyclopropenium salt. A fine filter was used to remove solid AgCl and the solution was washed with H ₂ 0 (2 x 100 mL). The organic layer was concentrated and filtered again. It was then dried in vacuo to yield a yellow liquid (5.06 g, 79.0%). 'H, ^,3 C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl with an additional peak in the ^,3 C NMR due to DC A.

(22) Tris(diburylamino)cyclopropenium nitrate, [C ₃ (NBu ₂ ) ₃ ]N0 ₃

[C ₃ (NBu ₂ ) ₃ ]Cl (5.24 g, 1 1.5 mmol) was stirred with HN0 ₃ (10 mL, 69%, 153 mmol) in H ₂ 0 (20 mL). The product was extracted with dichloromethane (75 mL) and washed again with HN0 ₃ (10 mL, 69%, 153 mmol). The organic layer was then washed with H ₂ 0 (3 x 75 mL) until the pH was neutral and dried in vacuo to yield an orange liquid (4.16 g, 75.2%). ¾, ¹³ C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl.

(23) Tris(dibutylamino)cycIopropenium tetrafluoroborate, [C ₃ (NBu ₂ ) ₃ ]BF ₄

[C ₃ (NBu ₂ ) ₃ ]Cl (6.17 g, 13.6 mmol) was stirred with HBF ₄ (20 mL, 35%, 110 mmol) in H ₂ 0 (50 mL). The product was extracted with dichloromethane (75 mL) and washed again with HBF ₄ (20 mL, 35%, 110 mmol). The organic layer was then washed with H ₂ 0 (3 x 50 mL) until the pH was neutral and dried in vacuo to yield an orange liquid (4.13 g, 79.6%). Ή, ^, C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl.

(24) Tris(dibutylamino)cyclopropenium trifiuoromethanesulfonate, [C ₃ (NBu ₂ ) ₃ ]OTf

[C ₃ (NBu ₂ ) ₃ ]Cl (6.00 g, 13.2 mmol) was stirred with LiOTf (2.25 g, 14.5 mmol) in H ₂ 0 (100 mL). The product was extracted with dichloromethane (75 mL), washed with H ₂ 0 (5 x 100 mL), and dried in vacuo to yield a yellow solid (5.95 g, 79.4%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl with an additional peak in the ¹³ C NMR due to OTf. (25) Tris(diethanolamino)cyclopropenium chloride, [C ₃ (N(CH ₂ CH ₂ OH) ₂ ) ₃ ]Cl

HN(CH ₂ CH ₂ OH) ₂ (97.1 g, 0.925 mol) was mixed with CH ₂ C1 ₂ (250 mL), and the suspension was cooled to 0 °C. C ₃ CI ₅ H (24.7 g, 0.115 mol) was added dropwise and the solution stirred overnight. The mixture was heated to reflux for 24 h. CH ₂ C1 ₂ was then removed in vacuo. The mixture was dissolved into ethanol (150 mL) and molecular sieves (13X, 10 A pore size) were added slowly until the solution was completely absorbed into the sieves. Two further portions of ethanol (100 mL), were added and then soaked up by more molecular sieves. The molecular sieves were soaked in ethanol for 3 h, then overnight in ethanol. This was repeated twice, soaking overnight in methanol. Alcohol was removed in vacuo, yielding a pale yellow viscous liquid (24 g in total). All four fractions were approximately 90% tris(diethanolamino)cyclopropenium chloride, with 10% [H ₂ N(CH ₂ CH ₂ 0H) ₂ ]C1. Molecular sieves were washed with excess H ₂ 0, and the process was repeated to remove [H ₂ N(CH ₂ CH ₂ 0H) ₂ ]C1, which gave a pale yellow viscous liquid (7 g, 15.8%). Ή NMR (D ₂ 0, 300 MHz) δ 3.81 (t, ³ J _m = 5.3 Hz, 12H, NCH ₂ ), 3.61 ppm (t, ³ J _HH = 5.3 Hz, 12H, NCH ₂ CH ₂ ).

(26) Tris(diethanolamino)c clopropenium fluoride, [C ₃ (N(CH ₂ CH ₂ OH)2)3]F The sample of [C ₃ (N(CH ₂ CH ₂ OH) ₂ ) ₃ ]Cl, prepared as described above, was dissolved into water (250 mL), and Ag ₂ 0 (7.0 g, 0.030 mol) added and stirred for 3 h in a blacked out flask. AgCl was removed by filtration through Celite. The solution was then neutralized to pH 7.5 with aqueous HF. H ₂ 0 was partially (200 mL) removed in vacuo. Complete drying was achieved with additions (3 x 150 mL, 3 x 50 mL) of ethanol and wo-propanol, followed by extended drying under a high vacuum, with stirring and mild heat (40 °C). ¹⁹ F NMR (282 MHz, D ₂ 0) δ 122.05 (s). ¹³ C NMR (75 MHz, D ₂ 0, acetonitrile added as reference): δ 1 18.18 (C ₃ ), 59.38 (NCH ₂ CH ₂ OH), 54.29 (N H ₂ CH ₂ OH).

(27) Tris(diaUylamino)cyclopropenium chloride, [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]CI

C ₃ C1 ₅ H (6.67 g, 31.1 mmol) and HN(CH ₂ CHCH ₂ ) ₂ (23.6 g, 243 mmol) gave a yellow liquid (9.95 g, 88.9% yield) after separation from diallylammonium chloride using option (i) with chloroform. ^] H NMR (500 MHz, CDC1 ₃ ): δ 5.58 (m, 6H, NCH ₂ CHCH ₂ ), 5.04 (m, 12H, NCH ₂ CHCH ₂ ), 3.76 (d, ³ J _HH = 5.14 Hz, 13H, NCH ₂ CHG¾). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 130.81 (NCH ₂ HCH ₂ ), 1 18.39 (NCH ₂ CH H ₂ ), 116.36 (C ₃ ), 54.03 (NC¾CHCH ₂ ). ES-MS ⁺ : m/z 324 (100%, M ⁺ ).

(28) Tris(diallylamino)cyclopropeiiium bromide, [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]Br

[C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]C1 (1.07 g, 2.98 mmol) was stirred with HBr (7 mL, 38%, 44 mmol). The product was extracted with dichloromethane (2 x 25 mL), washed twice more with HBr (5 mL, 38%, 33 mmol), washed with H ₂ 0 (4 x 50 mL) until the pH was neutral, and then dried in vacuo to yield a dark brown solid (0.8 g, 66.6%). ^I3 C NMR and MS ⁺ as for [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]C1. (29) Tris(diallylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ ( (CH ₂ CHCH ₂ ) ₂ ) ₃ ]TFSA

[C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]C1 (4.11 g, 11.4 mmol) was stirred with LiTFSA (7.00 g, 24.4 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (2 x 100 mL), washed with H ₂ 0 (3 x 100 mL), and then dried in vacuo to yield a light yellow liquid (5.00 g, 72.4%). Ή, ¹³ C NMR and MS ⁺ as for

[C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]C1 with an additional peak in the ¹ C NMR due to TFSA.

(30) Tris(diallylamino)cyclopropenium dicyanoamide, [C ₃ ( (CH ₂ CHCH ₂ ) ₂ ) ₃ ]DCA

[C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]C1 (5.19 g, 14.4 mmol) was stirred with NaDCA (2.84 g, 31.9 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (2 x 100 mL), washed with H ₂ 0 (3 x 100 mL), and then dried in vacuo to yield a light yellow liquid (5.06 g, 89.9%). Ή, ¹³ C NMR and MS ⁺ as for

[C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]C1 with an additional peak in the ¹³ C NMR due to DC A.

(31) Tris(butylmethylamino)cyclopropenium chloride, [C ₃ (NBuMe) ₃ ]Cl

C ₃ C1 ₅ H (25.0 g, 117 mmol) and HNBuMe ₂ (81.0 g, 929 mmol) gave a light yellow liquid (35.0 g, 90.9% yield) after separation of butylmethylammonium chloride using option (iii) then (i) with chloroform. It was then washed with diethyl ether (2 x 100 mL) and petroleum ether (2 x 75 mL) to remove residual amine. Ή NMR (500 MHz, CDC1 ₃ ): 5 3.29 (t, ³ J _HH = 7.8 Hz, 6H, NG¾), 3.12 (s, 9H, NCH ₃ ), 1.56 (m, 6H, NCH ₂ C¾), 1.27 (m, 6H, NCH ₂ CH ₂ CH ₂ ), 0.88 (t, ³ J _HH = 7.5 Hz, 9H, CH ₂ CH ₃ ). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 1 16.75 (C ₃ ), 55.32 (NCH ₂ ), 40.18 (NCH ₃ ), 29.89 (NCH ₂ H ₂ ), 19.71 (NCH ₂ CH ₂ H ₂ ), 13.64 (CH ₂ H ₃ ). ES-MS ⁺ : m/z 294.29 (100%, M ⁺ ). (32) Tris(butylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NBuMe) ₃ ]TFSA

[C ₃ (NBuMe) ₃ ]Cl (3.00 g, 9.10 mmol) was stirred with LiTFSA (5.00 g, 17.4 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (50 mL), washed with H ₂ 0 (3 x 50 mL) and was dried in vacuo to yield a yellow liquid (3.90 g, 74.6%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBuMe) ₃ ]Cl with an additional peak in the ¹³ C NMR due to TFSA.

(33) Tris(burylmethylamino)cyclopropenium dicyanoamide, [C ₃ (NBuMe) ₃ ]DCA

[C ₃ (NBuMe) ₃ ]Cl (5.30 g, 16.1 mmol) was stirred with NaDCA (3.65 g, 41.0 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (50 mL), washed with H ₂ 0 (3 x 50 mL) and dried in vacuo to yield a yellow liquid (5.40 g, 93.3%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBuMe) ₃ ]Cl with an additional peak in the ¹³ C NMR due to DCA. (34) Tris(butylmethylamino)cyclopropenium nitrate, [C ₃ (NBuMe) ₃ ]N0 ₃

[C ₃ (NBuMe) ₃ ]Cl (3.49 g, 10.6 mmol) was stirred with HN0 ₃ (0.8 mL, 69%, 12.3 mmol) in H ₂ 0 (20 mL). The product was extracted with chloroform (3 x 20 mL), washed twice more with HN0 ₃ (0.8 mL, 69%, 12.3 mmol) in H ₂ 0 (20 mL), washed with H ₂ 0 (6 x 30 mL) until the pH was neutral, and was dried in vacuo to yield a brown liquid (3.51 g, 93.0%). Ή, ^l3 C NMR and MS ⁺ as for [C ₃ (NBuMe) ₃ ]Cl.

(35) Tris(butylmethylamino)cyclopropenium tetrafluoroborate, [C ₃ (NBuMe) ₃ ]BF ₄

[C ₃ (NBuMe) ₃ ]Cl (2.02 g, 6.13 mmol) was stirred with HBF ₄ (1.3 mL, 35%, 7.23 mmol) in H ₂ 0 (15 mL). The product was extracted with chloroform (3 x 10 mL), and washed twice more with HBF ₄ (1.3 mL, 35%, 7.23 mmol) in H ₂ 0 (15 mL). It was then washed with H 0 (3 x 30 mL) until the pH was neutral and was dried in vacuo to yield a brown liquid (2.19 g, 93.9%). Ή, ¹³ C NMR and MS ⁺ as for

[C ₃ (NBuMe) ₃ ]Cl.

(36) Tris(butylmethylamino)cyclopropeniuni thiocyanate, [C ₃ (NBuMe) ₃ ]SCN

[C ₃ (NBuMe) ₃ ]Cl (3.50 g, 10.6 mmol) was stirred with NaSCN (0.86 g, 10.6 mmol) in H ₂ 0 (20 mL). The product was extracted with chloroform (20 mL), washed twice with additional NaSCN (0.86 g, 10.6 mmol) and H ₂ 0 (20 mL), washed with H ₂ 0 (4 x 30 mL), and dried in vacuo to yield a brown liquid (3.97 g, 95.5%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBuMe) ₃ ]Cl with an additional peak in the ¹³ C NMR due to SCN.

(37) Tris(octadecylmethylamino)cycIopropenium chloride, [C ₃ (NStMe) ₃ ]Cl

C ₃ C1 ₅ H (2.92 g, 13.6 mmol), HNMe(C ₁₈ H ₃₇ ) (11.6 g, 40.9 mmol) and NEt ₃ (14.5 g, 143 mmol) gave a light yellow solid (10.2 g, 81.4% yield) after separation from methyloctadecylammonium chloride using option (i) with chloroform. The product was washed with petroleum ether (2 x 50 mL) to remove residual amine and dried in vacuo. ¾ NMR (300 MHz, CDC1 ₃ ): δ 3.33 (t, ³ / _HH = 7.6 Hz, 6H, NCH ₂ C ₁₇ H ₃₅ ), 3.17 (s, 9H, NCH , 1.60 (m, 6Η, NCH ₂ CH C ₁₆ H ₃₃ ), 1.12-34 (m, 90H, NC ₂ H4Ci ₅ H5 ₀ CH ₃ ), 0.85 (t, ³ J _HH = 6.5 Hz, 9H, NC17H34CH3). ¹³ C NMR (75 MHz, CDC1 ₃ ): δ 116.99 (C ₃ ), 55.70 (NCH ₂ ), 40.31 (NCH ₃ ), 31.90, 28.72-30.42, 28.05, 26.66, 22.66, 14.10 (CH ₃ ). ES-MS ⁺ : m/z 882.95 (100%, M ⁺ ).

(38) Tris(octadecylmethylamino)cyclopropeniuni bis(trifluoromethanesulfonyl)amide,

[C ₃ (NStMe) ₃ ]TFSA

[C ₃ (NStMe) ₃ ]Cl (4.00 g, 4.35 mmol) was stirred with LiTFSA (5.00 g, 17.4 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (100 mL), washed with H ₂ 0 (3 x 50 mL) and dried in vacuo to yield a yellow liquid (4.30 g, 84.9%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NStMe) ₃ ]Cl with an additional peak in the ¹³ C NMR due to TFSA. (39) Tris(octadecylmethylamino)cyclopropenium dicyanoaraide, [C ₃ (NStMe) ₃ ]DCA

[C ₃ (NStMe) ₃ ]Cl (3.00 g, 3.38 mmol) was stirred with NaDCA (1.20 g, 13.5 mmol) in H ₂ 0 (100 mL). The product was extracted with dichloromethane (100 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield a yellow solid (2.20 g, 68.5%). Ή, ^,3 C NMR and MS ⁺ as for [C ₃ (NStMe) ₃ ]Cl with an additional peak in the ¹³ C NMR due to DC A.

(40) Bis(diethylamino)dimethylaminocyclopropenium methylsulfate, [C ₃ (NEt ₂ ) ₂ (NMe ₂ )]MeS0 ₄

Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (8.91 g, 45.5 mmol), Me ₂ S0 ₄ (8.60 g, 68.2 mmol) and HNMe ₂ (6.80 g, 150 mmol) were reacted as described in the general synthetic procedure and gave a yellow liquid (5.72 g, 37.6%). Ή NMR (300 MHz, CDC1 ₃ ): δ 3.68 (s, 3H, MeS0 ₄ ), 3.40 (q, ³ J _HH = 7.3 Hz, 8H, NC¾CH ₃ ), 3.17 (s, 6H, NC¾), 1.27 (t, ³ J _HH = 7.2 Hz, 12H, NCH ₂ CH _? ). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 117.83 (CO, 1 16.31 (C ₂ ), 54.02 (CH ₃ S0 ₄ ), 47.28 (NCH ₂ CH ₃ ), 42.07 (CH ₃ ), 14.07 (NCH ₂ CH ₃ ).

(41) Bis(diethylamino)dimethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NEt ₂ ) ₂ (NMe ₂ )]TFSA

[C ₃ (NEt ₂ ) ₂ (NMe ₂ )]MeS0 ₄ (2.74 g, 8.18 mmol) was stirred with LiTFSA (8.0 g, 28.0 mmol) in H ₂ 0 (200 mL). The product was extracted with Et ₂ 0 (200 mL), washed with H ₂ 0 (3 x 200 mL) and dried in vacuo to yield a pale yellow liquid (2.63 g, 63.7%). ES-MS ⁺ : m/z 224.21 (100%, M ⁺ ). Ή and ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (NMe ₂ )]MeS0 ₄ with an alternative peak in the ¹³ C NMR due to TFSA replacing MeS0 ₄ .

(42) Bis(diethylamino)dimethyIaminocyclopropenium dicyanoamide, [C ₃ (NEt ₂ ) ₂ (NMe ₂ )]DCA

[C ₃ (NEt ₂ ) ₂ (NMe ₂ )]MeS0 ₄ (4.34 g, 13.0 mmol) was stirred with NaDCA (5.60 g, 62.9 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (100 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield a pale yellow liquid (3.24 g, 86.0%). Ή and ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (NMe ₂ )]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to DC A. MS ⁺ as for

[C ₃ (NEt ₂ ) ₂ (NMe ₂ )]TFSA.

(43) Bis(diethylamino)dibutylaminocycIopropenium methylsulfate, [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]MeS0 ₄ Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (6.23 g, 31.8 mmol), Me ₂ S0 ₄ (4.40 g, 34.9 mmol) and HNBu ₂ (4.91 g, 38.0 mmol) were reacted as described in the general synthetic procedure and gave a dark orange liquid (6.31 g, 47.4%). Ή NMR (300 MHz, CDC1 ₃ ): δ 3.69 (s, 3H, MeS0 ₄ ), 3.40 (q, J _HH = 7.1 Hz, 8H, NC¾CH ₃ ), 3.28 (t, ³ JHH = 7.91 Hz, 4H, NCH ₂ CH ₂ ), 1.60 (m, 4H, NCH ₂ G¾), 1.19-39 (m, 16H, NCH ₂ CH ₂ C¾ and NCH ₂ CH), 0.93 (t, ³ JHH = 7.33 Hz, 6H, CH ₂ CH ₂ CHj). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 116.76 (Q), 116.64 (C ₂ ), 54.35 (CH ₃ S0 ₄ ), 53.17 (NCH ₂ CH ₂ ), 47.35 (NCH ₂ CH ₃ ), 31.28 (NCH ₂ CH ₂ ), 20.10

(NCH ₂ CH ₂ CH ₂ ), 14.54 (NCH ₂ CH ₃ ), 14.00 (CH ₂ CH ₂ CH ₃ ). (44) Bis(diethylamino)diburylaminocyclopropenium bis(trifluoromerhanesulfonyl)amide,

[C ₃ (NEt ₂ ) ₂ (NBu ₂ )]TFSA

[C ₃ (NEt ₂ ) ₂ (NBu ₂ )]MeS04 (7.35 g, 17.5 mmol) was stirred with LiTFSA (10.0 g, 34.8 mmol) in H ₂ 0 (150 niL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (3 x 150 mL) and dried in vacuo to yield a dark orange liquid (6.71 g, 65.2%). ¾ and ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to TFSA.

(45) Bis(diethylamino)dibuty]aminocyclopropenium dicyanoamide, [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]DCA

[C ₃ (NEt ₂ ) ₂ (NBu ₂ )]MeS0 ₄ (6.31 g, 15.0 mmol) was stirred with NaDCA (4.00 g, 44.9 mmol) in H ₂ 0 (150 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (3 x 150 mL) and dried in vacuo to yield a dark orange liquid (5.05 g, 90.0%). Ή and ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to DC A.

(46) Bis(diethylamino)dihexyIaminocyclopropenium methylsulfate, [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]MeS0 ₄

Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (5.53 g, 28.2 mmol), Me ₂ S0 ₄ (5.33 g, 42.3 mmol) and HNHex ₂ (9.03 g, 48.7 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (10.9 g, 81.1 %). ¾ NMR (300 MHz, CDC1 ₃ ): δ 3.69 (s, 3H, MeS0 ₄ ), 3.41 (q, V _HH = 7.3 Hz, 8H, NC¾CH ₃ ), 3.27 (t, ³ J _HH = 8.5 Hz, 4H, NCH ₂ C ₅ H„), 1.60 (m, 4H, NCH ₂ CH ₂ C ₄ H ₉ ), 1.19-35 (m, 24H,

N(CH ₂ ) ₂ (CH ₂ ) ₃ CH ₃ and NCH ₂ CH)), 0.86 (t, ³ J _HH = 6.5 Hz, 6H, -N(C ₅ U _W )CH ₃ ). ^I C NMR (75 MHz, CDC1 ₃ ): δ 116.45 (C,), 116.38 (C ₂ ), 54.26 (CH ₃ S0 ₄ ), 53.17 (NCH ₂ C ₅ H _U ), 47.10 (N H ₂ CH ₃ ), 31.39 (NCH ₂ CH ₂ C ₄ H ₉ ), 29.02 (NC ₂ H ₄ CH ₂ C ₃ H ₇ ), 26.25 (NC ₃ H ₆ H ₂ C ₂ H5), 22.47 14.29 (NCH ₂ CH ₃ ), 13.91 (NC ₅ H ₁₀ CH ₃ ).

(47) Bis(diethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NEt ₂ ) ₂ (NHex ₂ )]TFSA

[C ₃ (NEt ₂ ) ₂ (NHex ₂ )]I samples contaminated with (Et ₂ N) ₂ C ₃ 0, prepared by treatment of (Et ₂ N) ₂ C ₃ 0 with excess Etl followed by removal of Etl by washing with diethylether, addition of HNHex ₂ , and further washing with diethylether, were combined and a large excess of LiTFSA (20 g, 69.7 mmol) in H ₂ 0 (300 mL) was added. The product was extracted with chloroform (300 mL) and washed with H ₂ 0 (2 x 300 mL). (Et ₂ N) ₂ C ₃ 0 was removed by washing with petroleum ether : diethylether (1 : 1 , 3 x 100 mL) and the product was dried in vacuo to yield a dark brown liquid (4 g). Ή and ¹³ C NMR as for

[C ₃ (NEt ₂ ) ₂ (NHex ₂ )]MeS0 but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to TFSA. (48) Bis(diethylamino)dihexylaminocyclopropenium dicyanoamide, [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]DCA

[C ₃ (NEt ₂ ) ₂ (NHex ₂ )]MeS04 (10.9 g, 22.9 mmol) was stirred with NaDCA (7.50 g, 84.2 mmol) in H ₂ 0 (150 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (4 x 100 mL) and dried in vacuo to yield an orange liquid (8.86 g, 90%). Ή and ¹³ C NMR as for

[C ₃ (NEt ₂ ) ₂ (NHex ₂ )]MeS04 but with no peaks due to MeS0 ₄ and an additional peak in the ¹ C NMR due to DC A.

(49) Bis(diethylamino)diethanolaminocyclopropenium iodide, [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ 0H) ₂ )]I

Cyclopropenone (Et ₂ N)2C30 (7.68 g, 39.2 mmol) was dried using ethanol azetropes (5 x 50 mL).

Iodoethane (97.5 g, 625 mmol) was added and the solution was heated to reflux for 18 h. It was then cooled to ambient temperature and HN(C ₂ H ₄ OH) ₂ (8.44 g, 80.3 mmol) was added and stirred at ambient temperature 48 h. Excess iodoethane was removed in vacuo and H ₂ 0 (100 mL) added. Cyclopropenone was extracted with dichloromethane (100 mL and 50 mL) and the combined extracts were washed with H ₂ 0 (2 x 100 mL). The H ₂ 0 washings were combined with the main product H ₂ 0 layer and were then extracted with dichloromethane (3 x 100 mL) to yield a yellow liquid (3.50 g, 21.7%). Ή NMR (300 MHz, D ₂ 0): δ 3.73 (t, V _HH = 5.3 Hz, 4H, NCH ₂ C¾OH), 3.47 (t, V _HH = 5.3 Hz, 4H, NCH ₂ CH ₂ OH), 3.37 (q, ³ J _HH = 7.1 Hz, 8H, NCH ₂ CH ₃ ), 1.17 (t, V _HH = 7.1 Hz, 12H, NCH ₂ C¾). ¹³ C NMR (75 MHz, D ₂ 0, methanol added as reference): δ 1 17.89 (C,), 117.26 (C ₂ ), 59.46 (NCH ₂ CH ₂ OH), 54.38 (NCH ₂ CH ₂ OH), 47.20 (N H ₂ CH ₃ ), 13.98 (NCH ₂ H ₃ ). MS ⁺ as for [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]MeS0 ₄ .

(50) Bis(diethylamino)diethanolaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]TFSA

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]I (3.50 g, 8.52 mmol) was stirred with LiTFSA (5.0 g, 17 mmol) in H ₂ 0 (150 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (4 x 150 mL) and dried in vacuo to yield a yellow liquid (3.5 g, 73%). Ή and ¹³ C NMR as for

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]I with an additional peak at 119.8 in the ¹³ C NMR spectrum due to TFSA. MS ⁺ as for [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]MeS0 ₄ .

(51) Bis(diethylamino)diethanolaminocyclopropenium fluoride, [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]F

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]I (3.50 g, 8.52 mmol) was stirred in H ₂ 0 (250 mL), in a blacked-out flask, to which Ag ₂ 0 (3.0 g, 13 mmol) was added. After stirring for 3 h, AgCl precipitated and was removed by filtration through Celite. The solution was then neutralized to pH 7.5 with aqueous HF and reduced in volume to 20 mL in vacuo, with drying being completed with ethanol azetrope drying (3 x 200 mL) to yield a viscous yellow liquid (2.5 g, 96%). ¹⁹ F NMR (282 MHz, D ₂ 0, C ₆ H ₅ F reference): δ 121.94 (s). (52) Bis(diethylamino)diethanolaminocyclopropenium methyls ulfate,

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]MeS04

Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (8.88 g, 45.3 mmol), Me ₂ S0 ₄ (8.53 g, 67.6 mmol) and HN(C ₂ H ₄ OH) ₂ (8.10 g, 77.0 mmol) were reacted as described in the general synthetic procedure and gave a yellow liquid (6.40 g, 35.8%). Separation from the ammonium species and cyclopropenone was carried out by dissolution into H ₂ 0 (75 mL), and extraction of cyclopropenone and [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]MeS0 ₄ with dichloromethane (8 x 75 mL). [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]MeS0 ₄ was then extracted using H ₂ 0 (3 x 50 mL). Ή NMR (500 MHz, CDC1 ₃ ): δ 3.82 (t, ³ J _HH = 4.9 Hz, 4H, NCH ₂ CH ₂ OH), 3.66 (s, 3H, MeS0 ₄ ), 3.51 (t, ³ J _HH = 4.9 Hz, 4H, NCH ₂ CH ₂ OH), 3.42 (q, V _HH = 7.1 Hz, 8H, NC¾CH ₃ ), 1.25 (t, ³ J _HH = 7.1 Hz, 12H, NCH ₂ CH ₃ ). ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]I with an additional peak in the ¹³ C NMR spectrum due to MeS0 ₄ . ES-MS ⁺ : m/z 284.23 (M ⁺ , 100%).

(53) Bis(diethylamino)diallylaminocyclopropeniuni methyls ulfate,

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CHCH ₂ ) ₂ )]MeS0 ₄

Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (7.54 g, 38.5 mmol), Me ₂ S0 ₄ (6.27 g, 49.7 mmol) and HN(CH ₂ CHCH ₂ ) ₂ (6.30 g, 64.8 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (7.44 g, 50%). Ή NMR (CDC1 ₃ , 500 MHz): 8 5.81 (m, 2H, NCH ₂ CH=CH ₂ ), 5.28 (d, ³ J _HH = 10.5 Hz, 2H, NCH ₂ CH=CH ₂ ), 5.25 (d, ³ J _HH = 17 Hz, 2H, NCH ₂ CH=CH ₂ ), 3.92 (d, ³ J _HH = 5.5 Hz ,4H,

NCH ₂ CH=CH ₂ ), 3.68 (s, 3H, CH ₅ S0 ₄ ), 3.35 (q, ³ J _HH = 7 Hz, 8H, NCH ₂ CH ₃ ), 1.23 (t, ³ J _HH = 7 Hz,12H, NCH ₂ CH ₃ ). '¾{Ή} NMR (CDC1 ₃ , 126 MHz): δ 131.34 (NCH ₂ HCH ₂ ), 1 18.60 (NCH ₂ CH H ₂ ), 1 16.48 (ring C), 116.15 (ring C), 54.34 (NCH ₂ CHCH ₂ ), 54.04 (MeS0 ₄ ), 46.95 (NCH ₂ CH ₃ ), 13.97 (NCH ₂ H ₃ ) ₂ . ES-MS ⁺ : m/z 276.245 (M ⁺ , 100%).

(54) Bis(diethylamino)diallylaminocyclopropeiiium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CHCH ₂ ) ₂ )]TFSA

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CHCH ₂ ) ₂ )]MeS0 ₄ (7.44 g, 19.2 mmol) was stirred with LiTFSA (3 equivalents) in H ₂ 0 (100 mL). The product was extracted with chloroform (100 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield an orange liquid (7.0 g, 84%). ¾, ¹³ C NMR and MS ⁺ as for

[C ₃ (NEt ₂ ) ₂ (N(CH ₂ CHCH ₂ ) ₂ )]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to TFSA.

(55) Bis(diethylamino)butylmethylaminocyclopropenium methyls ulfate,

[C ₃ (NEt ₂ ) ₂ (NBuMe)]MeS0 ₄

Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (6.41 g, 32.7 mmol), Me ₂ S0 ₄ (8.26 g, 65.5 mmol) and HNBuMe (7.14 g, 81.9 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (9.70 g, 78.6%). Using an alternative route, to a stirred solution of [C ₃ (NEt ₂ ) ₂ (NHBu]MeS0 ₄ (1.0 g, 2.8 mmol) in dry THF at -78 °C was slowly added n-BuLi (1.89 mL, 3.03 mmol). The reaction was then stirred for 6 h and brought to room temperature. Me ₂ S0 ₄ (0.33 mL, 2.76 mmol) was added to this solution and stirred for 1 h. The solvent was removed in vacuo, the oil was washed with dry diethyl ether several times, the product was then dissolved in chloroform and filtered to remove LiMeS0 ₄ . Removal of solvent in vacuo gave an orange oil (0.90 g, 87%).

Ή NMR (300 MHz, CDC1 ₃ ): δ 3.66 (s, 3H, MeS0 ₄ ), 3.39 (q, ³ J _HH = 7.3 Hz, 8H, NCH ₂ CH ₃ ), 3.30 (t, ³ J _HH = 7.9 Hz, 2H, NC¾CH ₂ ), 3.13 (s, 3H, NCHj), 1.59 (m, 2Η, NCH ₂ G¾), 1.19-38 (m, 14H, NCH ₂ CH ₂ CH ₂ and NCH ₂ G¾), 0.92 (t, V _HH = 7.3 Hz, 3H, CH ₂ CH ₃ ). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 117.20 (C,), 116.14 (C ₂ ), 55.16 (N H ₂ CH ₂ ), 54.04 (CH ₃ S0 ₄ ), 47.18 (N H ₂ CH ₃ ), 39.53 (NCH ₃ ), 30.01 (NCH ₂ H ₂ ), 19.72 (NCH ₂ CH ₂ H ₂ ), 14.14 (NCH ₂ H ₃ ), 13.68 (CH ₂ CH ₂ C¾).

(56) Bis(diethylamino)butylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C ₃ (NEt ₂ ) ₂ (NBuMe)] TFS A

[C ₃ (NEt ₂ ) ₂ (NBuMe)]MeS0 ₄ (3.90 g, 10.3 mmol) was stirred with LiTFSA (10 g, 34.8 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield an orange liquid (4.48 g, 79.3%). Ή and ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (NBuMe)]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to TFS A.

(57) Bis(diethylamino)buty lmethylaminocyclopropenium dicyanoamide,

[C ₃ (NEt ₂ ) ₂ (NBuMe)]DCA [C ₃ (NEt ₂ ) ₂ (NBuMe)]MeS0 ₄ (5.50 g, 14.6 mmol) was stirred with NaDCA (4.00 g, 44.9 mmol) in H ₂ 0 (100 mL). The product was extracted with chloroform (100 mL), washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield an orange liquid (4.10 g, 84.6%). Ή and ^l3 C NMR as for

[C ₃ (NEt ₂ ) ₂ (NBuMe)]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to DC A. (58) Bis(diethyIamino)hexylmeth\ aminocyclopropenium methyls ulf ate,

[C ₃ (NEt ₂ ) ₂ (NHexMe)]MeS0 ₄

Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (4.77 g, 24.3 mmol) and dimethylsulfate (3.68 g, 29.1 mmol) were mixed at ambient temperature for 30 min. Hexylmethylamine (3.45 g, 29.9 mmol) was added and the solution stirred at ambient temperature for 30 min. The product was washed with pentane (3 x 75 mL), to remove excess hexylmethylamine, and then with diethylether (3 x 75 mL), to remove residual

bis(diethylamino)cyclopropenone. The product was then dissolved in CHC1 ₃ (100 mL) and washed with H ₂ 0 (3 x 100 mL). CHC1 ₃ was removed in vacuo to yield an orange liquid (7.70 g, 78.2%). ^! H NMR (300 MHz, CDC1 ₃ ): δ 3.67 (s, 3H, MeSQ ₄ ), 3.40 (q, ³ J _HH = 7.2 Hz, NCH ₂ CH ₃ ), 3.30 (t, ³ J _HH = 7.8 Hz, NCH ₂ (CH ₂ ) ₄ CH ₃ ), 3.14 (s, NG¾), 1.55-69 (m, NCH ₂ CH (CH ₂ ) ₃ CH ₃ ), 1.19-36 (m, NCH ₂ C¾ and N(CH ₂ ) ₂ (CH ₂ ) ₃ CH ₃ ), 0.85 (t, ³ J _HH = 6.9 Hz, NCH ₂ (CH ₂ ) ₄ CH ₃ ). ¹³ C NMR (75 MHz, CDC1 ₃ ): δ 117.36 (C), 116.40 (C ₂ ), 55.73 (N H ₂ C ₅ H„), 54.04 (MeS0 ₄ ), 47.39 (N H ₂ CH ₃ ), 39.66 (NCH ₃ ), 31.63

(NCH ₂ H ₂ C ₄ H ₉ ), 28.21 (N(C ₂ H ₄ ) H ₂ C ₃ H ₇ ), 26.45 (NC ₃ H ₆ H ₂ C ₂ H ₅ ), 22.72 (NC ₄ H ₈ H ₂ CH ₃ ), 14.25 (NCH ₂ H ₃ ), 14.16 (NC ₅ H ₁₀ H ₃ ).

(59) Bis(diethylamino)hexylmethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C ₃ (NEt ₂ ) ₂ (NHexMe)]TFSA

[C ₃ (NEt ₂ ) ₂ (NHexMe)]MeS0 ₄ (3.10 g, 7.65 mmol) was stirred with LiTFSA (7.20 g, 25.08 mmol) in H ₂ 0 (150 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (3 x 150 mL) and dried in vacuo to yield a yellow liquid (3.60 g, 82.0%). Water content: 173.1 ppm. Ή and ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (NHexMe)]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR at 119.85 (q, 'JcF = 321.6 Hz, CF ₃ ), due to TFSA.

(60) Bis(diethylamino)hexylmethylaminocyclopropenium dicyanoamide,

[C ₃ (NEt ₂ ) ₂ (NHexMe)]DCA [C ₃ (NEt ₂ ) ₂ (NHexMe)]MeS0 ₄ (4.60 g, 11.4 mmol) was stirred with NaDCA (3.40 g, 38.2 mmol) in H ₂ 0 (150 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (3 x 150 mL) and dried in vacuo to yield a yellow liquid (3.75 g, 91.6%). Ή and ¹ C NMR as for

[C ₃ (NEt ₂ ) ₂ (NHexMe)]MeS0 ₄ but with no peaks due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to DC A. (61) Bis(diethylamino)butylaminocyclopropenium methylsulfate, [C ₃ (NEt ₂ ) ₂ (NHBu)]MeS0 ₄

Cyclopropenone (Et ₂ N) ₂ C ₃ 0 (9.00 g, 45.9 mmol), Me ₂ S0 ₄ (8.70 g, 69.0 mmol) and H ₂ NBu (4.37 g, 59.7 mmol) were reacted as described in the general synthetic procedure and gave an orange liquid (10.46 g, 62.7%). Before H ₂ NBu was added, the product was washed with dry diethyl ether (5 x 20 mL) to remove unreacted Me ₂ S0 ₄ . Ή NMR (500 MHz, CDC1 ₃ ): δ 8.14 (br, 1H, NH), 3.67 (s, 3H, CH ₃ S0 ₄ ), 3.35 (q, H _H = 7.16 Hz, 2H, NCH ₂ CH ₃ ), 3.20 (t, ³ J _HH = 6.83 Hz, 2H, NCH ₂ CH ₂ ), 1.61 (m, 2H, NCH ₂ CH ₂ ), 1.33 ( m, 2Η, NCH ₂ CH ₂ CH ₂ ), 1.21 (t, ³ J _HH = 7.25 Hz, 3H, NCH ₂ CH ₃ ), 0.87 (t, ³ J _HH = 7.25 Hz, 3H,

CH ₂ CH ₂ CH ₃ ). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 115.94 (equivalent C ₃ atoms), 1 14.65 (br, unique C ₃ atom), 53.92 (CH ₃ S0 ₄ ), 46.79 (N H ₂ CH ₂ ), 46.27 (NCH ₂ CH ₃ ), 32.044 (NCH ₂ CH ₂ ), 19.46

(NCH ₂ CH ₂ CH ₂ ), 13.95 (NCH ₂ CH ₃ ), 13.34 (CH ₂ CH ₂ H ₃ ). (62) Bis(diethylamino)burylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NEt ₂ ) ₂ (NHBu)]TFSA

[C ₃ (NEt ₂ ) ₂ (NHBu)]MeS0 ₄ (3.40 g, 9.37 mmol) was stirred with LiTFSA (8.10 g, 28.2 mmol) in H ₂ 0 (150 mL). The product was extracted with chloroform (150 mL), washed with H ₂ 0 (2 x 100 mL) and dried in vacuo to yield an orange liquid (3.67 g, 73.7%). Ή and ¹³ C NMR similar to

[C ₃ (NEt ₂ ) ₂ (NHBu)]MeS0 ₄ with some differences: Ή NMR NH resonance at 6.22 ppm. ¹³ C NMR resonance for TFSA at 119.79 ppm (q, 'JcF = 322 Hz, CF ₃ ), C ₃ ring resonances at 115.40 (equivalent C ₃ atoms) and 1 15.37 (unique C ₃ atom) ppm.

(63) Bis(diethylamino)burylaminocyclopropenium dicyanoamide, [C ₃ (NEt ₂ ) ₂ (NHBu)]DCA [C ₃ (NEt ₂ ) ₂ (NHBu)]MeS0 ₄ (5.92 g, 16.3 mmol) was stirred with NaDCA (4.37 g, 49.1 mmol) in H ₂ 0

(150 mL). The product was extracted with chloroform (2 x 100 mL), washed with H ₂ 0 (4 x 100 mL) and dried in vacuo to yield an orange liquid (3.36 g, 64.8%). Ή and ¹ C NMR similar to

[C ₃ (NEt ₂ ) ₂ (NHBu)]MeS0 ₄ with some differences: Ή NMR resonance for NH at 7.92 ppm. ^,3 C NMR resonance for DCA at 1 19.39 ppm, C ₃ ring resonances at 1 15.54 (equivalent C ₃ atoms) and 114.81 (slightly br, unique C ₃ atom) ppm.

(64) Bis(diethylamino)-iS'-(l-carboxylethylamino)cyclopropenium methylsulfate,

[C ₃ (NEt ₂ ) ₂ (NH((S)-CHMeCOOH))]MeS0 ₄

Dried bis(diethylamino)cyclopropenone (21.13 g, 108 mmol) was stirred with Me ₂ S0 ₄ (13.3 mL, 140 mmol) for 30 minutes. The mixture was washed with dry diethyl ether several times to remove excess Me ₂ S0 ₄ and cyclopropenone. This gave [C ₃ (NEt ₂ )(OMe)]MeS0 ₄ as an orange viscous oil (24.2 g, 70%). [C ₃ (NEt ₂ ) ₂ (OMe)]MeS0 ₄ (11.37 g, 35.31 mmol) was stirred with L-alanine (4.1 g, 46 mmol) and NEt ₃ (17 mL, 106 mmol) in water (20 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-alanine. The solvent was removed in vacuo and NEt ₃ was removed by washing with dry diethylether (5 x 50 mL) to yield an orange oil (10.4 g, 75.7%). Ή NMR (500MHz, CDC1 ₃ ): δ 8.36 (d, ³ J _HH = 7 Hz, 1H, NH), 5.65 (br, 1H, COOH), 4.01 (dq, ³ J _HH = 7 Hz, J _HH = 7 Hz, 1H, CH), 3.71 (s, 3H, MeS0 ₄ ), 3.38 (q, ³ J _HH = 6.6 Hz, 8H, NCH ₂ CH ₃ ), 1.58 (d, ³ J _HH = 7 Hz, 3H, Me), 1.24 (t, ³ J _HH = 6.6 Hz, 12H, NCH ₂ CH ₃ ). ¹³ C NMR (CDC1 ₃ , 126 MHz) δ 175.37 (COOH), 1 15.75 (unique ring C), 115.18 (equivalent ring C), 56.54 (CHMe), 54.74 (MeS0 ₄ ), 46.54 (N H ₂ CH ₃ ), 18.34 (CH H ₃ ), 14.22 (NCH ₂ H ₃ ). EI-MS: m/z 268.93 (M ⁺ ). (65) Bis(dus0-propylamino)dibutylaimnocydopropenium chloride, [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]Cl

C ₃ C1 ₅ H (5.00 g, 23.4 mmol) was stirred at 0 °C in dry dichloromethane (75 mL). HN(i-Pr) ₂ (11.9 g, 1 18 mmol) added dropwise over 1 h followed by stirring for 2 h at 0 °C and then overnight at ambient temperature. HNBu ₂ (12.3 g, 95.0 mmol) was added dropwise over 1 h, followed by stirring for 2 h at 0 °C, then overnight at ambient temperature. The product was separated from ammonium chloride salts using option (iv) and then (i) using dichloromethane. Drying in vacuo yielded a colourless solid (5.77 g, 61.9%). Ή NMR (300 MHz, CDC1 ₃ ): δ 3.79 (spt, ³ J _HH = 13.8 Hz, 4H, NCH(CH ₃ ) ₂ ), 3.36 (t, ³ J _HH = 7.9 Hz, 4H, NCH ₂ ), 1.53 (m, 4Η, NCH ₂ CH ₂ ), 1.30 (d, V _HH = 7.0 Hz, 24H, NCH(CH ₂ ), 1.23 (m, 4Η, NCH ₂ CH ₂ CH ₂ ), 0.89 (t, ³ J _HH = 7.90 Hz, 6H, CH ₂ CHj). ^I C NMR (75 MHz, CDC1 ₃ ): & 118.46 (d), 1 17.49 (C ₂ ), 51.57 (N H ₂ ), 51.50 (N H(CH ₃ ) ₂ ), 30.77 (NCH ₂ CH ₂ ), 21.99 (NCH(CH ₃ ) ₂ ), 19.44

(CH ₂ CH ₃ ), 13.67 (CH ₂ CH ₃ ).

(66) Bis(diethylamino)cyclopropenone, (Et ₂ N) ₂ C ₃ 0

KOH (300 g) was dissolved into water (4 L). Tris(diethylamino)cyclopropenium chloride (42 g, 0.15 mol) was added to the solution, and heated to 70 °C for 18 h. Organic compounds were extracted from aqueous solution using CH ₂ C1 ₂ (3 x 250 mL). CH ₂ C1 ₂ removed in vacuo and neutralized using a small amount of HCl. Ethanol (25 mL) added to allow filtering to remove an insoluble impurity, followed by removal of the ethanol in vacuo. Addition of acetone (75 mL) precipitated KC1, which was filtered off. Acetone was removed in vacuo, yielding a dark orange liquid (22 g, 77%). Ή NMR (300 MHz, CDC1 ₃ ): δ 3.21 (q, ³ J _HH = 7.2 Hz, 8H, NCH ₂ CH ₃ ), 1.20 (t, ³ 7 _H H = 7.2 Hz, 12H, NCH ₂ CH ₃ ). ¹³ C NMR (75 MHz, CDC1 ₃ ): δ 133.74 (CO), 119.32 (C ₂ ), 46.01 (NCH ₂ CH ₃ ), 14.18 (NCH ₂ CH ₃ ).

(67) Tris(dipentylamino)cyclopropenium chloride, [C ₃ (NPent ₂ )3]Cl

Dipentylamine (11.9 g, 75.9 mmol) and NEt ₃ (25 mL, 179 mmol) were added to CH ₂ C1 ₂ (100 mL) and cooled to 0 °C. C ₃ C1 ₅ H (4.84 g, 22.6 mmol) was added dropwise and the solution stirred overnight at ambient temperature. The solution was heated to reflux for 4 h, and then H ₂ 0 (200 mL) was added. The solution was acidified with aqueous HCl. The CH ₂ C1 ₂ was separated and washed with H ₂ 0 (3 x 150 mL). Removal of CH ₂ C1 ₂ in vacuo yielded a viscous orange liquid (10.6 g, 90.4% yield). Ή NMR (500 MHz, CDC1 ₃ ): δ 3.25 (t, ³ J _HH = 7.70 Hz, 12 H, NCH ₂ ), 1.57 (m, 12 Η, NCH ₂ CH ₂ ), 1.30 (m, 12 Η,

NCH ₂ CH ₂ CH ₂ ), 1.21 (m, 12 Η, NCH ₂ CH ₂ CH ₂ CH ₂ ), 0.85 (t, ³ J _HH = 7.15 Hz, 18 H,

NCH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ). ^, C NMR (126 MHz, CDC1 ₃ ): 8 1 16.30 (C ₃ ), 52.86 (N H ₂ ), 28.50 (NCH ₂ CH ₂ ), 28.45 (NCH ₂ CH ₂ CH ₂ ), 22.16 (NCH ₂ CH ₂ CH ₂ H ₂ ), 13.67 (NCH ₂ CH ₂ CH ₂ CH ₂ H ₃ ). ES-MS ⁺ : m/z 504.5265 (100%, M ⁺ ).

(68) Tris(dipentylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NPent ₂ ) ₃ ]TFSA

[C ₃ (NPent ₂ ) ₃ ]Cl (3.09 g, 5.73 mmol) was stirred with aqueous LiTFSA (4.9 g, 19.9 mmol) in water (100 mL). The product was extracted with Et ₂ 0 (200 mL), and additional LiTFSA (6.1 g, 21.3 mmol) and H ₂ 0 (100 mL) were added. The Et ₂ 0 was then washed was H ₂ 0 (3 x 100 mL) and dried in vacuo to yield an orange liquid (4.30 g, 95.7%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NPent ₂ ) ₃ ]Cl with additional peaks in the ¹ C NMR due to TFSA.

(69) Tris(dipentylaniino)cyclopropenium dicyanoamide, [Cj(NPent ₂ ) ₃ ]DCA

[C ₃ (NPent ₂ ) ₃ ]Cl (4.13 g, 7.66 mmol) was stirred with aqueous NaDCA (3.8 g, 43.1 mmol) in water (100 mL). The product was extracted with Et ₂ 0 (200 mL), and additional NaDCA (6.1 g, 44.9 mmol) and H ₂ 0 (100 mL) were added. The Et ₂ 0 was then washed was H ₂ 0 (3 x 100 mL) and dried in vacuo to yield an orange liquid (3.69 g, 84.5%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NPent ₂ ) ₃ ]Cl with additional peaks in the ¹³ C NMR due to DC A.

(70) Tris(dihexyIamino)cyclopropenium chloride, [C ₃ (NHex ₂ ) ₃ ]Cl Dihexylamine (20.8 g, 112 mmol) and NEt ₃ (45 mL, 323 mmol) were added to CH ₂ C1 ₂ (200 mL) and cooled to 0 °C. C ₃ C1 ₅ H (4.84 g, 22.6 mmol) was added dropwise and the solution stirred overnight at ambient temperature. The solution was heated to reflux for 4 h, then washed with H ₂ 0 (4 x 200 mL). The solution was acidified with aqueous HC1. The CH ₂ C1 ₂ was separated and washed with H ₂ 0 (4 x 200 mL). Removal of CH ₂ C1 ₂ in vacuo gave a viscous orange liquid (11.8 g, 83.4% yield). Ή NMR (500 MHz, CDC1 ₃ ): δ 3.29 (t, ³ J _HH = 8.07 Hz, 12 H, NCH ₂ ), 1.60 (m, 12 Η, NCH ₂ CH ₂ ), 1.28 (m, 36 Η,

NCH ₂ CH ₂ (CH ₂ ) ₃ ), 0.86 (t, 6.60 Hz, 18 H, N(CH ₂ ) ₅ CH3). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 1 16.55 (C ₃ ), 53.14 (NCH ₂ ), 31.46 (NCH ₂ H ₂ ), 28.98 (N(CH ₂ ) ₂ CH ₂ ), 26.34 (N(CH ₂ ) ₃ CH ₂ ), 22.50 (N(CH ₂ ) ₄ H ₂ ), 13.88 (N(CH ₂ ) ₅ CH ₃ ). MS ⁺ as for [C ₃ (NHex ₂ ) ₃ ]TFSA.

(71) Tris(dihexylamino)cyclopropenium bis(trifluoromethanesuIfonyl)amide, [C ₃ (NHex ₂ )3]TFSA [C ₃ (NHex ₂ ) ₃ ]Cl (3.12 g, 5.00 mmol) was stirred with LiTFSA (4.0 g, 14.0 mmol) in water (50 mL). The product was extracted with CH ₂ C1 ₂ (25 mL) and washed with H ₂ 0 (50 mL). Additional LiTFSA (4.0 g,

14.0 mmol) and H ₂ 0 (100 mL) were added. The product was extracted with Et ₂ 0 (100 mL), washed with H ₂ 0 (4 x 100 mL) and dried in vacuo to yield an orange liquid (3.91 g, 89.9%). Ή and ¹³ C NMR as for [C ₃ (NHex ₂ ) ₃ ]Cl with additional peaks in the ^l3 C NMR due to TFSA. ES-MS ⁺ : m/z 588.6 (100%, M ⁺ ). (72) Tris(dihexylamino)cyclopropenium dicyanoamide, [C ₃ (NHex ₂ ) ₃ ]DCA

[C ₃ (NHex ₂ ) ₃ ]Cl (3.85 g, 6.16 mmol) was stirred with NaDCA (2.5 g, 28.1 mmol) in water (50 mL). The product was extracted with CH ₂ C1 ₂ (25 mL) and washed with H ₂ 0 (50 mL). Additional NaDCA (2.5 g,

28.1 mmol) and H ₂ 0 (100 mL) were added. The product was extracted with Et ₂ 0 (100 mL), washed with H ₂ 0 (4 x 100 mL) and dried in vacuo to yield an orange liquid (3.61 g, 89.4%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NHex ₂ ) ₃ ]Cl with additional peaks in the ¹³ C NMR due to DC A. (73) Tris(didecylamino)cyclopropenium chloride, [C ₃ (NDec ₂ ) ₃ ]Cl

Didecylamine (13.8 g, 46.3 mmol) and Et ₃ (15 mL, 108 mmol) were added to CH ₂ C1 ₂ (100 mL) and cooled to 0 °C. C ₃ C1 ₅ H (2.84 g, 13.2 mmol) was added dropwise and the solution stirred overnight at ambient temperature. The solution was heated to reflux for 6 h, then H ₂ 0 was added (200 mL). The solution was acidified with aqueous HC1, separated and washed again with dilute aqueous HC1. The CH ₂ C1 ₂ was separated and washed with H ₂ 0 (3 x 150 mL). Removal of CH ₂ C1 ₂ in vacuo yielded a viscous orange liquid and white precipitate. After addition of acetone and cooling in the freezer, the precipitate was removed by filtration through silica gel three times. Removal of acetone in vacuo yielded an orange liquid (9.46 g, 74.5% yield). Ή NMR (500 MHz, CDC1 ₃ ): δ 3.26 (t, ³ J _HH = 7.70 Hz, 12 H, NCH ₂ ), 1.57 (m, 12 Η, NCH ₂ CH ₂ ), 1.23 (m, 84 Η, N(CH ₂ ) ₂ (CH ₂ ) ₇ ), 0.83 (t, ³ J _HH = 6.97 Hz, 18 H,

N(CH ₂ ) ₉ CH ₃ ). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 1 16.49 (C ₃ ), 53.1 1 (NC¾), 31.78 (NCH ₂ H ₂ ), 29.50 (N(CH ₂ ) ₂ CH ₂ ), 29.44 (N(CH ₂ ) ₃ CH ₂ ), 29.34 (N(CH ₂ ) ₄ H ₂ ), 29.21 (N(CH ₂ ) ₅ H ₂ ), 29.01 (N(CH ₂ ) ₆ H ₂ ), 26.66 (N(CH ₂ ) ₇ H ₂ ), 22.57 (N(CH ₂ ) ₈ CH ₂ ), 14.00 (N(CH ₂ ) ₉ CH ₃ ). ES-MS ⁺ : m/z 924.9965 (100%, M ⁺ ).

(74) Tris(didecylamino)cyclopropenium bis(rrifluoromethanesulfonyl)amide, [C ₃ (NDec ₂ ) ₃ ]TFSA [C ₃ (NDec ₂ ) ₃ ]Cl (3.05 g, 3.18 mmol) was stirred with LiTFSA (4.0 g, 14.0 mmol). H ₂ 0 (100 mL) was added and product extracted with Et ₂ 0 (200 mL). Additional LiTFSA (4.0 g, 14.0 mmol) and H ₂ 0 (100 mL) were added. The solution was again extracted with Et ₂ 0 and washed with H ₂ 0 (3 x 100 mL) before drying in vacuo to yield an orange liquid (3.18 g, 83.0%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NDec ₂ ) ₃ ]Cl with additional peaks in the ¹³ C NMR due to TFSA. (75) Tris(didecylamino)cyclopropenium dicyanoamide, [C ₃ (NDec ₂ ) ₃ ]DCA

[C ₃ (NDec ₂ ) ₃ ]Cl (3.10 g, 3.23 mmol) was stirred with aDCA (2.0 g, 22.5 mmol). H ₂ 0 (100 mL) was added and the product was extracted with Et ₂ 0 (200 mL). Additional NaDCA (2.0 g, 22.5 mmol) and H ₂ 0 (100 mL) were added. The solution was again extracted with Et ₂ 0 and then washed with H ₂ 0 (3 x 100 mL) and dried in vacuo to yield an orange liquid (3.10 g, 96.8%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NDec ₂ ) ₃ ]Cl with additional peaks in the ^,3 C NMR due to DC A.

(76) Bis(di .w-propylamino)dibutylaminocyclopropeniuni bis(trifluoromethanesulfonyl)amide, [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]TFSA

[C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]Cl (0.302 g, 0.755 mmol) was stirred with LiTFSA (0.650 g, 2.27 mmol) in water (50 mL). The product was extracted with CHC1 ₃ (50 mL). Additional LiTFSA (0.804 g, 2.81 mmol) in H ₂ 0 (50 mL) was added. The CHC1 ₃ solution was separated and then washed with H ₂ 0 (3 x 50 mL) and dried in vacuo to yield a colourless solid (0.30 g, 61.7%). Ή and ¹³ C NMR as for [C ₃ (N'Pr ₂ ) ₂ (NBu ₂ )]Cl with additional peaks in the ¹ C NMR due to TFSA. (77) Bis(dif.sO-propylaraino)dibur> aminocyclopropeniura dicyanoamide,

[C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ ))DCA

[C ₃ (N(i-Pr) ₂ )2(NBu ₂ )]Cl (0.300 g, 0.750 mmol) was stirred with NaDCA (0.350 g, 3.93 mmol) in water (50 mL). The product was extracted with CHC1 ₃ (50 mL). Additional NaDCA (0.519 g, 5.83 mmol) in H ₂ 0 (50 mL) was added. The CHC1 ₃ solution was separated and then washed with H ₂ 0 (3 x 50 mL) and dried in vacuo to yield a colourless solid (0.25 g, 77.5%). Ή and ^{l 3} C NMR as for

[C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]Cl with additional peaks in the ^,3 C NMR due to DC A.

(78) Bis(diethylamino)hexylaminocyclopropenium methylsulfate, [C ₃ (NEt ₂ ) ₂ (NHHex)]MeS0 ₄

Dried cyclopropenone (Et ₂ N) ₂ C ₃ 0 (4.61 g, 23.5 mmol) and dimethylsulfate (5.93 g, 47.0 mmol) were mixed at ambient temperature for 1 h. Hexylamine (15.32 g, 151 mmol) was added and the solution was stirred at ambient temperature for 3 h. The product was washed with diethyl ether :petroleum ether (1 :1, 3 x 75 mL). The product was then dissolved in H ₂ 0 (50 mL), acidified with aqueous HC1, extracted with CH ₂ C1 ₂ (50 mL) and washed with H ₂ 0 (3 x 75 mL). CH ₂ C1 ₂ was removed in vacuo, and the product was then washed with diethyl ether (4 x 50 mL). Aqueous NaOH (200 mL, 0.38 mol/L) was added, and the product was washed with pet ether (4 x 100 mL) and diethyl ether (3 x 100 mL). The product was acidified with aqueous HC1 and H ₂ 0 removed in vacuo. Addition of acetone caused precipitation of NaCl, which was filtered off. Removal of acetone in vacuo yielded a yellow liquid (2.64 g, 33.9%). Ή NMR (500 MHz, CDC1 ₃ ): δ 9.04 (br. s, 1H, NH), 3.69 (s, (CH ₃ )S0 ₄ ), 3.39 (br. q, _H = 7.0 Hz,

NCH ₂ CH ₃ ), 3.19 (q, ³ J _HH = 7.0 Hz, NCH ₂ (CH ₂ ) ₄ CH ₃ ), 1.65 (m, NCH ₂ CH ₂ (CH ₂ ) ₃ CH ₃ ), 1.18-35 (m, NCH ₂ CH5 and N(CH ₂ ) ₂ (CH ₂ ) ₃ CH ₃ ), 0.82 (t, V _HH = 6.8 Hz, NCH ₂ (CH ₂ ) ₄ C¾). ¹³ C NMR (125 MHz, CDC1 ₃ ): 1 16.93 (d and C ₂ ), 54.61 (CH ₃ S0 ₄ ), 47.64 (NCH ₂ C ₅ Hn), 46.82 (NCH ₂ CH ₃ ), 31.65

(NCH ₂ CH ₂ C ₄ H ₉ ), 30.67 (N(C ₂ H ₄ )CH ₂ C ₃ H ₇ ), 26.69 (NC ₃ H ₆ CH ₂ C ₂ H ₅ ), 22.74 14.53 (NCH ₂ CH ₃ ), 14.123(NC ₅ H ₁₀ CH ₃ ). MS ⁺ as for [C ₃ (NEt ₂ ) ₂ (NHHex)]TFSA.

(79) Bis(diethylamino)hexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NEt ₂ ) ₂ (NHHex)]TFSA

[C ₃ (NEt ₂ ) ₂ (NHHex)]MeS0 ₄ (2.64 g, 7.97 mmol) was stirred with LiTFSA (6.9 g, 24.1 mmol) in H ₂ 0 (200 mL) for 30 min. The product was extracted with diethyl ether (200 mL). Additional LiTFSA (6.3 g, 22.0 mmol) and H ₂ 0 (200 mL) were added and the mixture stirred for 1.5 h. The organic layer was washed with H ₂ 0 (4 x 75 mL) and dried in vacuo to yield a yellow liquid (3.50 g, 78.4%). Ή and ¹³ C NMR as for [C ₃ (NEt ₂ ) ₂ (NHHex)]MeS0 ₄ but with no peaks due to MeS0 ₄ and additional peaks in the ¹³ C NMR due to TFSA. ES-MS ⁺ : m/z 280.3 (100%, M ⁺ ). (80) Bis(diethylamino)aminocyclopropenium methyls ulfate, [C ₃ (NEt ₂ ) ₂ (NH _z )]MeS0

NH ₃ ( _g) (excess) was passed through a rapidly stirred sample of [C ₃ (NEt ₂ ) ₂ (OMe)]MeS0 ₄ (3 g, 9 mmol) for 2 h. Excess NH ₃ was removed in vacuo to yield an orange viscous oil (2.86 g, 100%). Ή NMR (500 MHz, D ₂ 0): δ 3.60 (s, 3H, CH ₃ S0 ₄ ), 3.24 (q, ³ J _HH = 7.3 Hz , 8H, NCH ₂ CH ₃ ), 1.08 (t, ³ J _HH = 7.3 Hz, 12H, NCH ₂ CH ₃ ). Ή NMR (500 MHz, CDC1 ₃ ): δ 7.18 (s, 2H, NH), 3.77 (s, 3Η, CH ₃ S0 ₄ ), 3.39 (q, ³ J _HH = 7 Hz , 8H, NCH ₂ CH ₃ ), 1.23 (t, ³ J _HH = 7 Hz, 12H, NCH ₂ CH ₃ ). ^,3 C NMR (126 MHz, D ₂ 0) δ 116.57 (equivalent ring C), 113.97 (unique ring C), 55.55 (CH ₃ S0 ₄ ), 46.42 (NCH ₂ CH ₃ ), 13.80 (NCH ₂ H ₃ ). EI-MS: m/z 196.18 (M ⁺ ).

(81) Bis(diethylamino)aminocyclopropenium bis(trifluoromethanesulfonyl)amide,

[C ₃ (NEt ₂ ) ₂ (NH ₂ )]TFSA

[C ₃ (NEt ₂ ) ₂ (NH ₂ )]MeS0 ₄ (2.35 g, 8 mmol) was stirred with LiTFSA (6.58 g, 24 mmol) in water (10 mL) for 30 min. The product was extracted with chloroform (3 x 10 mL) to yield a yellow oil (2.83 g, 78%). Ή NMR (500 MHz, CDC1 ₃ ): 8 5.83 (s, 2H, NH), 3.36 (q, ³ J _HH = 7 Hz , 8H, NCH ₂ CH ₃ ), 1.25 (t, ³ J _HH = 7 Hz, 12H, NCH ₂ CH ₃ ). ^l C NMR (126 MHz, CDC1 ₃ ) δ 120.74 (q, = 299 Hz, CF ₃ ), 116.23 (equivalent ring C), 114.18 (unique ring C), 46.80 (N H ₂ CH ₃ ), 14.40 (NCH ₂ H ₃ ). EI-MS: m/z 196.18 (M ⁺ ).

(82) Trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide, [C ₃ (NPhH) ₃ ]TFSA

[C ₃ (NPhH) ₃ ]Cl (2 g, 6 mmol) was stirred with LiTFSA (4.95 g, 18 mmol) in water (10 mL) for 1 h. The product was extracted with dichloromethane (3 x 10 mL) to yield yellow crystals (3 g, 88%). Ή NMR (500 MHz, CDCN ₃ ): δ 8.8 (br, 1H, NH), 7.52 (dt, ³ J _HH = 8Hz, 2H, Ph), 7.32 (t, ³ J _HH = 8 Hz, 1H, Ph), 7.28 (dd, ³ J _HH = 8 Hz, 2H, Ph). ¹³ C NMR (126 MHz, CD ₃ CN): δ 138.44 (ipso-P ), 130.32 (m-Ph), 125.30 (p- Ph), 118.45 (o-Ph), 113.05 (C ₃ ). EI-MS: m/z 312.15 (M ⁺ ).

(83) Bis(diethylamino)butylaminocyclopropenium tetrafluoroborate, [C ₃ (NEt ₂ ) ₂ (NHBu)]BF ₄

Dried bis(diethylamino)cyclopropenone (1.03 g, 5 mmol) was stirred with [Me ₃ 0]BF ₄ (1.01 mL, 6.5 mmol) for 4 h to yield [C ₃ (NEt ₂ ) ₂ (OMe)]BF ₄ as a yellow oil (1.3 g, 83%). Butylamine (0.56 mL, 5.67 mmol) was then added and the mixture was stirred for 2 h. The product was washed several times with diethyl ether to remove unreacted amine. This yielded a yellow oil (1.2 g, 82%). Ή and ¹³ C NMR spectra as for [C ₃ (NEt ₂ ) ₂ (NHBu)]MeS0 ₄ but with no peaks due to MeS0 ₄ and an NH peak at 6.81 ppm.

(84) Bis(diethyIamino)dibutylaminocyclopropenium iodide, [C ₃ (N£t ₂ ) ₂ (NBu ₂ )]I

Dried bis(diethylamino)cyclopropenone (4.19 g, 21 mmol) and ethyl iodide (43 mL, 530 mmol) were heated to reflux for 20 h. Unreacted ethyl iodide was distilled out and the residue was washed with diethyl ether to yield [C ₃ (NEt ₂ ) ₂ (OEt)]I as a yellow solid (3.44 g, 45.65%). Dichloromethane (10 mL) and dibutylamine (2.14 mL, 13 mmol) were then added and the solution was stirred for 2 h. Dichloromethane was then removed in vacuo. The product was washed several times with diethyl ether to remove unreacted amine. This yielded a yellow solid (3 g, 71%). Ή NMR and ¹³ C NMR spectra as for [C ₃ (NEt ₂ )2(NBu2)]MeS04 but with no peaks due to MeS0 ₄ . (85) Tris(diethylamino)cyclopropenium iodide, [C ₃ (NEt ₂ ) ₃ ]I

[C ₃ (NEt ₂ )3]Cl (1.15 g, 4 mmol) was heated to reflux with ethyl iodide (6.43 mL, 80 mmol) for 20 h. Unreacted ethyl iodide was distilled out and the residue was dissolved in dichloromethane (20 mL) and washed with water (3 x 10 mL). Dichloromethane was removed in vacuo to yield orange crystals (1.2 g, 79%). ¾ ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₃ ]Cl. Anal, calcd for C ₁₅ H ₃₀ N ₃ I: I, 33.45. Found (ion chromatography): I, 32.35. Chloride content was determined by ion chromatography to be 14 ppm.

(86) Bis(diethyIamino)dihexylaminocyclopropenium iodide, [C ₃ (NEt ₂ )2(NHex ₂ )]I

Dihexylamine (1.72 mL, 7 mmol) was added to a solution of [C ₃ (NEt ₂ ) ₂ (OEt)]I (2 g, 5.6 mmol) (prepared as described above for [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]I) in dichloromethane (10 mL) and stirred for 2 h.

Dichloromethane was removed in vacuo. The product was washed several times with diethyl ether to remove unreacted amine. This gave a yellow liquid (2.5 g, 87%). Ή and ^I3 C NMR as for

[C ₃ (NEt ₂ ) ₂ (NHex ₂ )]MeS0 ₄ with no peaks due to MeS0 ₄ .

(87) Tris(dimethylamino)cyclopropenium dicyanoamide, [C ₃ (NMe ₂ ) ₃ ]DCA

[C ₃ (NMe ₂ ) ₃ ]Cl (4.35 g, 21 mmol) was stirred with NaDCA (5.68g, 64 mmol) in water (50 mL) at 40 °C overnight. The product was extracted with chloroform (3 x 10 mL). The solvent was removed in vacuo to yield a yellow solid (2.7g, 54%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NMe ₂ ) ₃ ]Cl with an additional peak in the ¹³ C NMR due to DC A.

(88) Tris(dimethylamino)cyclopropenium thiocyanate, [C ₃ (NMe ₂ ) ₃ ]SCN

[C ₃ (NMe ₂ ) ₃ ]Cl (4.5 g, 22 mmol) was stirred with NH ₄ SCN (5.68 g, 66 mmol) in water (50 mL) overnight. The product was extracted with chloroform (3 x 10 mL) and the solvent was removed in vacuo to yield a yellow solid (2.6 g, 52%). ¾, ¹³ C NMR and MS ⁺ as for [C ₃ (NMe ₂ ) ₃ ]Cl with an additional peak in the ¹³ C NMR due to SCN.

(89) Tris(dibutylamino)cyclopropeniuni tetracyanoborate, [C ₃ (NBu ₂ ) ₃ ]B(CN) ₄ l-Ethyl-3-methylimidazolium tetracyanoborate (2.43 g, 1 1 mmol) was stirred with [C ₃ (NBu ₂ ) ₃ ]Cl (5.62 g, 12 mmol) in water (50 mL) at 60 °C overnight. The product was extracted with diethyl ether (3 x 10 mL) and then washed with water. The solvent was removed in vacuo to yield a yellow liquid (4.86g, 81%). ¾, ¹³ C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl with additional peaks in the ¹ C NMR due to IB(CN) ₄ ] ^" at 122.66 ppm (q, 'j _CB = 71.6 Hz).

(90) Tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate,

[C ₃ (NBu ₂ ) ₃ ]FAP l-Ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (3.85 g, 7 mmol) was stirred with [C ₃ (NBu ₂ ) ₃ ]Cl (3.48 g, 8 mmol) in 50 mL of water at 60 °C overnight. The product was extracted with diethyl ether (3 x 10 mL) and then washed with water. The solvent was removed in vacuo to yield a yellow liquid (5.26 g, 88%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl.

(91) Tris(dihexylamino)cycIopropenium dibutylphosphate, [C ₃ (NHex ₂ ) ₃ ](BuO) ₂ P0 ₂ NaOH (2.56 g, 64.1 mmol) was dissolved in H ₂ 0 (200 mL) and dibutylphosphate (12.4 mL, 62.5 mmol) was added. [C ₃ (NHex ₂ ) ₃ ]Cl (6.44 g, 10.3 mmol) was stirred with half of this solution for 30 min. The product was extracted with diethyl ether (200 mL), and the diethyl ether solution was then stirred with the remainder of the sodium dibutylphosphate solution for 30 min. The diethyl ether layer was separated and washed with H ₂ 0 (3 x 100 mL). The solution was dried in vacuo to yield an orange liquid (7.64 g, 93.1%). Ή NMR (CDC1 ₃ , 500 MHz): δ 3.25 (t, 12H, NCH ₂ ), 3.25 (t, 4Η, PCH ₂ ), 1.57 (m, 12Η, NC¾CH ₂ ), 1.57 (m, 4Η, PCH ₂ CH ₂ ), 1.34 (m, 4Η, PCH ₂ CH ₂ CH ₂ ), 1.26 (s, 36Η,

NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ), 0.85 (m, 18Η, NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ), 0.85 (m, 6Η,

PCH ₂ CH ₂ CH ₂ CH ₃ ). ^,3 C NMR (CDC1 ₃ , 125 MHz): <5 116.52 (s, ring C), 64.61 (d, 'jpc = 5.65 Hz, P H ₂ ), 53.09 (N H ₂ ), 33.10 (d, ² J _PC = 7.63 Hz, PCH ₂ H ₂ ), 31.46 (NCH ₂ H ₂ ), 28.98 (NCH ₂ CH ₂ H ₂ ), 26.33 (NCH ₂ CH ₂ CH ₂ H ₂ ), 22.50 (NCH ₂ CH ₂ CH ₂ CH ₂ H ₂ ), 19.1 (PCH ₂ CH ₂ C¾), 13.93 (PCH ₂ CH ₂ CH ₂ H ₃ ), 13.87 (NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ). EI-MS: m/z 588.62 (M ⁺ ).

(92) Bis(diethylamino)-5-(l-carboxylethylamino)cyclopropenium

bis(trifluoromethanesulfonyl)amide, [C ₃ (NEt ₂ ) ₂ (NH((£)-CHMeCOOH))]TFSA

[C ₃ (NEt ₂ ) ₂ (NH((5)-CHMeCOOH))]MeS0 ₄ (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). 'H and ¹³ C NMR spectra similar to [C ₃ (NEt ₂ ) ₂ (NH((5)-CHMeCOOH))]MeS0 ₄ with no peaks due to MeS0 ₄ and additional peaks in the ¹³ C NMR due to TFSA. ES-MS ⁺ as for [C ₃ (NEt ₂ ) ₂ (NH((S)- CHMeCOOH))]MeS0 ₄ .

(93) Bis(diethylamino)-5'-(2-carboxypyrrolidino)cyclopropenium methylsulfate,

[C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]MeS0 ₄

[C ₃ (NEt ₂ ) ₂ (OMe)]MeS0 ₄ (5.65 g, 18 mmol) was stirred with L-proline (2.62 g, 23 mmol) and NEt ₃ (3.64 mL, 23 mmol) in water (20 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-proline. The mixture was dissolved in ice cold water and the product was extracted with chloroform: ethanol (2:1) (3 x 30 mL). The solvent was removed in vacuo to yield an orange oil (5.53 g, 78%). Ή NMR (400 MHz, CDC1 ₃ ): δ 7.37 (br, 1H, COOH), 4.42 (dd, ³ J _HH = 3.6Hz, , ³ J _HH = 8Hz, 1H, CH), 3.72 (m, 1H, NCH ₂ ), 3.68 (s, 3Η, CH ₃ S0 ₄ ), 3.60 (ddd, ³ J _HH = 7.9Hz, 1H, NCH ₂ ), 3.34 (m, 8Η, NCH ₂ CH ₃ ), 2.31 (m, 2H, NCH ₂ CH ₂ CH ₂ ), 2.01 (m, 2Η, NCH ₂ CH ₂ ), 1.21 (t, ³ J _HH = 6.6 Hz, 12H, NCH ₂ CH ₃ ). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 174.09 (COOH), 116.08 (equivalent ring C), 114.80 (unique ring C), 64.60 (NCH), 54.26 (CH ₃ S0 ₄ ), 51.89 (NCH ₂ ), 46.77 (NCH ₂ CH ₃ ), 31.13 (NCHCH ₂ ), 24.32 (NCH ₂ CH ₂ CH ₂ ), 13.94 (NCH ₂ CH ₃ ). EI-MS: m/z 295.00 (M ⁺ ).

(94) Bis(diethylamino)-5-(2-carboxypyrrolidino)cyclopropenium

bis(trifluoromethanesulfonyl)amide, [C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]TFSA

[C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]MeS0 ₄ (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). ¾ and ¹³ C NMR similar to [C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]MeS0 ₄ but with no peaks due to MeS0 ₄ and additional peaks in the ¹³ C NMR due to TFSA. ES-MS ⁺ as for [C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]MeS0 ₄ . (95) Bis(diethylamino)-5-(l-carboxy-2-methylpropylamino)cycloprop enium methylsulfate, [C ₃ (NEt ₂ ) ₂ (NH(C ₄ H ₈ COOH))]MeS0 ₄

[C ₃ (NEt ₂ ) ₂ (OMe)]MeS0 ₄ (15 g, 47 mmol) was stirred with L-valine (7.09 g, 61 mmol) and NEt ₃ (9.67 mL, 61 mmol) in water (50 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-valine. The mixture was dissolved in ice cold water and the product was extracted with chloroform: ethanol (2: 1) (3 x 30 mL). The solvent was removed in vacuo to yield a yellow solid (10.00 g, 55%). Ή NMR (400MHz, CDC1 ₃ ): δ 8.44 (br, 1H, NH), 3.67 (s, 3Η, CH ₃ S0 ₄ ), 3.62 (d, ³ J _HH = 6.4Hz, 1H, CH), 3.38 (m, 8Η, NCH ₂ CH ₃ ), 2.23 (m, 1H, CH), 1.22 (t, ³ J _HH = 7.2 Hz, 12H, NCH ₂ CH ₃ ), 1.03 (d, ³ J _HH = 6.8 Hz, 3H, CH ₃ ), 0.98 (d, ³ J _HH = 6.8 Hz, 3H, CH ₃ ). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 174.25 (COOH), 1 15.87 (equivalent ring C), 1 15.46 (unique ring C), 68.82 (CHNH), 54.27 (CH ₃ S0 ₄ ), 46.62 (NCH ₂ CH ₃ ), 31.00 (CH(CH ₃ ) ₂ ), 19.28 (C¾), 18.80 (C¾), 14.27 (NCH ₂ CH ₃ ). EI-MS: m/z 296.233 (M ⁺ ).

(96) Bis(diethylamino)- ₁ S'-(l-carboxy-2-methylpropylamino)cyclopropeniuiii

bis(trifluoromethanesulfonyl)amide, [C ₃ (NEt ₂ ) ₂ (NH(C ₄ H ₈ COOH))]TFSA

[C ₃ (NEt ₂ ) ₂ (NH(C4H ₈ COOH))]MeS0 ₄ (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). 'H and ¹³ C NMR spectra similar to [C ₃ (NEt ₂ ) ₂ (NH(C ₄ H ₈ COOH))]MeS0 ₄ but with no peaks due to MeS0 ₄ and additional peaks in the ¹ C NMR due to TFSA. ES-MS ⁺ as for [C ₃ (NEt ₂ ) ₂ (NH(C ₄ H ₈ COOH))]MeS0 ₄ . (97) Bis(diethylamino)-5'-(l-carboxy-2-hydroxylpropylamino)cyclop ropenium methyls ulf ate, [C ₃ (NEt2) ₂ (NH(C ₃ H ₅ OHCOOH))]MeS0 ₄

[C ₃ (NEt ₂ ) ₂ (OMe)]MeS04 (10 g, 31 mmol) was stirred with L-threonine (4.8 g, 40 mmol) and NEt ₃ (6.45 mL, 40 mmol) in water (50 mL) overnight. Water was removed in vacuo and the product was dissolved in acetone (20 mL) and filtered to remove unreacted L-threonine. The mixture was dissolved in ice cold water and the product was extracted with chloroform:ethanol (2:1) (3 x 30 mL). The solvent was removed in vacuo to yield a yellow solid (9.30 g, 76%). Ή NMR (500 MHz, CDC1 ₃ ): δ 8.04 (br, 1H, NH), 5.27 (br, 2Η, OH+H ₂ 0), 4.08 (m,lH, NCH), 3.69 (m, 1Η, CHOH), 3.67 (s, 3H, CH ₃ S0 ₄ ), 3.37 (q, ³ J _HH = 7.16 Hz , 8H, NCH ₂ CH ₃ ), 1.23 (d, ³ J _HH = 7.5 Hz, 3H, CH ₃ ), 1.21 (t, ³ J _HH = 7.25 Hz, 12H,

NCH ₂ CH ₃ ). ^,3 C NMR (126 MHz, CDC1 ₃ ) b 173.37 (COOH), 115.98 (equivalent ring C), 115.35 (unique ring C), 67.78 ( HCH ₃ ), 67.20 (CHNH), 54.31 (CH ₃ S0 ₄ ), 46.49 (NCH ₂ CH ₃ ), 19.42 (C¾), 14.20 (NCH ₂ H ₃ ). EI-MS: m/z 298.87 (M ⁺ ).

(98) Bis(diethylamino)-i_>-(l-carboxy-2-hydroxylpropylamino))c yclopropenium

bis(trifluoromethanesulfonyl)amide, [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₅ OHCOOH))]TFSA [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₆ OCOOH))]MeS0 ₄ (2.1 g, 5 mmol) was stirred with LiTFSA (4.71 g, 16 mmol) in 10 mL of water. Extraction with chloroform (3 x 10 mL) yielded the product (2.57 g, 86%). Ή and ¹³ C NMR spectra similar to [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₆ OCOOH))]MeS0 ₄ but with no peaks due to MeS0 ₄ and additional peaks in the ¹³ C NMR due to TFSA. MS ⁺ as for [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₆ OCOOH))]MeS0 ₄ .

(99) Tris(dibutylamino)cyclopropenium isocyanate, [C ₃ (NBii2)3]NCO [C ₃ (NBu ₂ ) ₃ ]Cl (4.92 g, 10.8 mmol) was stirred overnight with NaNCO (2.13 g, 32.8 mmol) in H ₂ 0 (15 mL). The product was extracted with CHC1 ₃ (3 x 20 mL) and dried in vacuo to yield a brown liquid (3.16 g, 63%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl with an additional peak in the ¹³ C NMR due to NCO.

(100) Tris(diburylamino)cyclopropenium trichlorostannate, [C ₃ (NBu ₂ ) ₃ ]SnCl ₃ [C ₃ (NBu ₂ ) ₃ ]Cl (3.53 g, 7.74 mmol) and SnCl ₂ .H ₂ 0 (1.75 g, 8.43 mmol) were each dissolved in 0.5N HCl (10 mL) and were separately heated to 50 °C. These solutions were then combined and kept at 50 °C for 2 h. An aqueous solution (20 mL) was then extracted with dichloromethane (3 x 10 mL) and dried in vacuo to yield a yellow product (3.12 g, 62%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NBu ₂ ) ₃ ]Cl. (101) Bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate,

[C ₃ (NEt ₂ ) ₂ (NHex ₂ )]OTf

Dried bis(diethylamino)cyclopropenone (1.14 g, 6 mmol) was stirred with MeCF ₃ S0 ₃ (0.8 mL, 8 mmol) in dry dichloromethane for 2 h. Solvent was removed in vacuo. The mixture was washed with dry diethyl ether several times to remove excess MeCF ₃ S0 ₃ and cyclopropenone. This gave an orange viscous oil of [C3(NEt ₂ )(OMe)]CF ₃ S0 ₃ , which was then stirred with Hex ₂ NH (1.23 mL, 5.2 mmol) for 2 h. The mixture was dissolved in chloroform: ethanol (2: 1 , 30 mL) and the product was washed with water (3 x 30 mL) to remove ammonium salts. Solvent was removed in vacuo to yield a brown oil (1.6 g, 77%). Ή, ¹³ C NMR and MS ⁺ as for [C ₃ (NEt ₂ ) ₂ NHex ₂ ]MeS0 ₄ but with no peaks in the Ή and ¹³ C NMR due to MeS0 ₄ and an additional peak in the ¹³ C NMR due to OTf.

(102) Bis(diethylamino)diiso-propylaminocyclopropemum methylsulfate,

[C ₃ (NEt ₂ ) ₂ (N(i-Pr) ₂ )]MeS0 ₄

[C ₃ (NEt ₂ ) ₂ (OMe)]MeS0 ₄ (7.0 g, 33 mmol), prepared by stirring bis(diethylamino)cyclopropenone with Me ₂ S0 ₄ as described for [C ₃ (NEt ₂ ) ₂ (NH((S)-CHMeCOOH))]MeS0 ₄ , was stirred with distilled (i-Pr) ₂ NH (33.93 g, 335 mmol) in an ice bath and then at ambient temperature for 18 h. The mixture was then heated to reflux for 3 h. Excess reagent was removed in vacuo. The mixture was dissolved in water (30 mL) and the product was extracted with dichloromethane (3 x 30 mL). Solvent was removed in vacuo and the product was washed with diethylether: dichloromethane (95:5, 3 x 15 mL) to yield an orange liquid (4.45 g, 33%). Ή, ¹³ C NMR and MS ⁺ as for [[C ₃ (NEt ₂ ) ₂ (N(i-Pr) ₂ )]DCA but with no peaks in the ¹³ C NMR due to DCA and additional peaks in the Ή and ¹³ C NMR due to MeS0 ₄ .

(103) Bis(diethylamino)diis0-propylaminocyclopropenium dicyanoamide,

[C ₃ (NEt ₂ ) ₂ (N(i-Pr) ₂ )]DCA

[C ₃ (NEt ₂ ) ₂ (N(i-Pr) ₂ )]MeS0 ₄ (4.45 g, 11.4 mmol) was stirred with NaDCA (6.02 g, 68 mmol) in H ₂ 0 (200 mL) for 40 minutes. The product was extracted with dichloromethane (3 x 20 mL), washed with H ₂ 0 (3 x 20 mL) and dried in vacuo to yield an orange liquid (3.67 g, 93%). Ή NMR (500 MHz,

CDC1 ₃ ): δ 3.75 (sept, ³ J _HH = 7.0 Hz, 2H, NCH(CH ₃ ) ₂ ), 3.70 (s, 3H, CH3SO4), 3.50 (q, ³ J _HH = 7.2 Hz, 8H, NCH ₂ ), 1.34 (d, ³ JHH = 7.0 Hz, 12H, CH(CH ₃ ) ₂ ), 1.29 (t, ³ J _HH = 7.2 Hz, 12H, CH ₂ CH ₃ ). ¹³ C NMR (126 MHz, CDCI ₃ ) δ 117.99 (C ₃ ), other C ₃ peak n.o., 54.46 (CH ₃ S0 ₄ ), 51.59 ( H(CH ₃ ) ₂ ), 49.67 (NCH ₂ ), 22.10 (CH(CH ₃ ) ₂ ), 14.55 (CH ₂ CH ₃ ). EI-MS: m/z 280.2752 (M ⁺ ). (104) Bis(dimethylamino)methoxycyclopropenium methylsulphate, [C ₃ (NMe ₂ )(OMe)]MeS0 ₄

Dried bis(dimethylamino)cyclopropenone (2.69 g, 19.2 mmol) was stirred with Me ₂ S0 ₄ (2.36 mL, 25 mmol) for 2 h. The mixture was washed with dry diethyl ether several times to remove methanol and excess dimethylsulfate. This gave an orange viscous oil (4.57 g, 90%). ^! H NMR (500 MHz, CDC1 ₃ ): δ 4.15 (s, 3H, OCH3), 3.63 (s, 3Η, CH ₃ SO ₄ ), 3.16 (s, 12Η, NCH ₃ ). ¹³ C NMR (126 MHz, CDC1 ₃ ) δ 122.76 (equivalent ring C), 119.89 (unique ring C), 63.87 (O H ₃ ), 54.17 (CH ₃ SO ₄ ), 41.13 (NCH ₃ ). EI-MS: m z 155.12 (M ⁺ ).

(105) Bis(dimethylamino)hexylmeth laniinocyclopropenium bis(trifluoromethanesulfony )amide, [C ₃ (NMe ₂ ) ₂ (NHexMe)]TFSA

[C3(NMe ₂ ) ₂ (OMe)]MeS0 ₄ (4.11 g, 15 mmol) was stirred with HexMeNH (2.88 mL, 19 mmol) in dry dichloromethane (10 mL) for 2 h. Dichloromethane was removed in vacuo. The mixture was dissolved in ice cold water and the product was extracted with chloroform: ethanol (2:1 , 3 x 30 mL). The solvent was removed in vacuo to yield [C ₃ (KMe ₂ ) ₂ (NHexMe)]MeS0 ₄ as a light yellow oil, which was stirred with LiTFSA (9.85g, 34 mmol) in H ₂ 0 (50 mL) for 30 min. The solvent was then removed in vacuo.

The mixture was dissolved in chloroform:ethanol (2:1 , 30 mL) and the product was washed with ice cold water (3 x 30 mL) to remove ammonium salts. Solvent was removed in vacuo and the product was dissolved in CHC1 ₃ (50 mL) and washed with water (3 x 50 mL). The solvent was removed in vacuo to yield a light yellow oil (5.62 g, 95%). Ή NMR (400 MHz, CDC1 ₃ ): δ 3.29 (t, ³ J _HH = 7.6 Hz, 2H, NCH ₂ ), 3.12 (s, 12Η, NCH ₃ ), 3.10 (s, 3Η, NCH ₃ ), 1.63 (m, 2Η, NCH ₂ CH ₂ ), 1.29 (m, 6Η,

NCH ₂ CH ₂ CH ₂ CH ₂ H ₂ H ₂ ), 0.88 (t, ³ J _HH = 6.8Hz, 6H, NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ). ¹³ C NMR (100 MHz, CDCI ₃ ): δ 1 19.91 (q, = 347 Hz, F ₃ ), 117.73 (equivalent ring C), 117.45 (unique ring C), 55.55 (N H ₂ ), 42.25 (N H ₃ ), 40.07 (N H ₃ ), 31.33 (NCH ₂ H ₂ ), 27.64 (NCH ₂ CH ₂ H ₂ ), 26.21

(NCH ₂ CH ₂ CH ₂ H ₂ ), 22.42(NCH ₂ CH ₂ CH ₂ CH ₂ H ₂ ), 13.88 (NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ H ₃ ). EI-MS: m/z 238.22 (M ⁺ ).

(106) Bis(dimethylamino)dihexylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C ₃ (NMe ₂ ) ₂ (NHex ₂ )]TFSA

[C ₃ (NMe ₂ ) ₂ (OMe)]MeS0 ₄ (2 g, 8 mmol) was stirred with Hex ₂ NH (2.3 mL, 10 mmol) in dry

dichloromethane (5 mL) for 2 h. Dichloromethane was removed in vacuo, the mixture was dissolved in ice cold water, and the product was extracted with chloroform:ethanol (2: 1 , 3 x 30 mL). The solvent was removed in vacuo to yield [C ₃ (NMe ₂ ) ₂ (NHex ₂ )]MeS04 as a light yellow oil, which was then stirred with LiTFSA (5.22g, 18 mmol) in H ₂ 0 (10 mL). The solvent was removed in vacuo, the mixture was dissolved in chloroform:ethanol (2:1 , 30 mL), and the product was washed with ice cold water (3 x 30 mL) to remove ammonium salts. The solvent was removed in vacuo to yield a light yellow oil (3 g, 80%). Ή NMR (400 MHz, CDC1 ₃ ): δ 3.28 (t, ³ J _HH = 8Hz, 4H, NCH ₂ ), 3.11 (s, 12Η, NCH ₃ ), 1.61 (m, 4Η, NCH ₂ CH ₂ ), 1.29 (m, 12Η, NCH ₂ CH ₂ CH ₂ CH ₂ H ₂ H ₂ ), 0.88 (t, 6.8Hz, 6H, NCH ₂

CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ). ¹³ C NMR (100 MHz, CDC1 ₃ ): δ 120.06 ( q, ^l J _CF = 347 Hz, CF ₃ ), 1 17.69

(equivalent ring C), 1 16.73 (unique ring C), 53.52 (NCH ₂ ), 42.18 (N H ₃ ), 31.32 (NCH ₂ H ₂ ), 28.55 (NCH ₂ CH ₂ H ₂ ), 26.23 (NCH ₂ CH ₂ CH ₂ H ₂ ), 26.23 (NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ), 26.23 (NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ H ₃ ). EI-MS: m/z 308.31 (M ⁺ ). (107) Bis(dimethylamino)dibutylaminocyclopropenium bis(trifluoromethanesulfonyl)amide, [C ₃ (NMe ₂ ) ₂ (NBu ₂ )]TFSA

[C ₃ (NMe ₂ )2(OMe)]MeS0 ₄ (2.4 g, 9 mmol) was stirred with Bu ₂ NH (1.97 mL, 12 mmol) in dry dichloromethane (5 mL) for 2 h. Dichloromethane was removed in vacuo and excess amine was removed by washing several times with dry diethylether to yield [C3(NMe ₂ )2(NBu ₂ )]MeS0 ₄ as a light yellow oil, which was then stirred with LiTFSA (6.92 g, 24 mmol) in H ₂ 0 (10 mL). The solvent was removed in vacuo, the mixture was dissolved in chloroform: ethanol (2:1, 30 mL), and the product was washed with ice cold water (3 x 30 mL) to remove ammonium salts. The solvent was then removed in vacuo to yield a light yellow oil (3.4 g, 80%). Ή NMR (400 MHz, CDC1 ₃ ): δ 3.28 (t, ³ J _HH = 7.6Hz, 4H, NCH ₂ ), 3.11 (s, 12Η, NCH ₃ ), 1.60 (m, 4Η, NCH ₂ CH ₂ ), 1.32 (m, 4Η, NCH ₂ CH ₂ CH ₂ ), 0.94 (t, ³ J _HH = 7.6Hz, 6H, NCH ₂ CH ₂ CH ₂ CH ₃ ). ¹³ C NMR (126 MHz, CDC1 ₃ ): δ 119.89 ( q, _F = 322 Hz, CF ₃ ), 117.59 (equivalent ring C), 116.66 (unique ring C), 53.22 (N H ₂ ), 42.17 (NCH ₃ ), 30.56 (NCH ₂ H ₂ ), 19.79 (NCH ₂ CH ₂ CH ₂ ), 13.65 (NCH ₂ CH ₂ CH ₂ H ₃ ). EI-MS: m/z 252.24 (M ⁺ ).

DSC, TGA and viscosity data for various of the triaminocyclopropenium salts discussed above are shown in Table 1 , in which T _g is the glass transition temperature, T _m the melting point, and T _d the thermal decomposition onset temperature. Microanalytical data are shown in Table 2, in which the first line in each row is the calculated value and the second line the value obtained on analysis. Conductivity data are shown in Table 3.

Table 1 : DSC, TGA and viscosity data

Compound T _m Td Viscosity Viscosity

(°C) ^fl (°C) ^a (°C)* (mPa.s (mPa.s at at 20°C) 60°C)

(1) [C ₃ (NMe ₂ ) ₃ ]Cl 32.5 78.3 221 - -

(2) [C ₃ (NMe ₂ ) ₃ ]TFSA n.o. 105.2 339 - -

(3) [C ₃ (NEt ₂ ) ₃ ]Cl n.o. 102.5 306 - -

(4) [C ₃ (NEt ₂ ) ₃ ]TFSA n.o. 17.7 393 143.5 21.8

(5) [C ₃ (NEt ₂ ) ₃ ]DCA n.o. 8.6 330 64.2 14.6

(6) [C ₃ (NEt ₂ ) ₃ ]N0 ₃ -66.1 40.7 330 395.4 46.9

(7) [C ₃ (NEt ₂ ) ₃ ]BF ₄ n.o. 26.9 377 207.4 28

(8) [C ₃ (NEt ₂ ) ₃ ]SCN -77.8 23.1 31 1 132.4 20.7

(9) [C ₃ (NEt ₂ ) ₃ ] ^-MeC ₆ H ₄ S0 ₃ 8 77.7 214 764.2 57.4 Compound T T„ Viscosity Viscosity

(°C) ^e (°C) ^e (°C)* (mPa.s (mPa.s at at 20°C) 60°C)

(10) [C ₃ (NEt ₂ ) ₃ ]OTf -0.2 50.3 345 -

(l l) [C ₃ (NPr ₂ ) ₃ ]Cl -30 80.9° 308 - . -

(12) [C ₃ (NPr ₂ ) ₃ ]TFSA -71.7 33.7 409 219.7 32.3

(13) [C ₃ (NPr ₂ ) ₃ ]DCA n.o. 52.9 317 - 14.6

(15) [C ₃ (NPr ₂ ) ₃ ]F.EtOH 49.6 14

(16) [C ₃ (NPr ₂ ) ₃ ]N0 ₃ -55.5 n.o. 311 - 141.4

(17) [C ₃ (NPr ₂ ) ₃ ]BF ₄ n.o. 80.9 397 - -

(18) [C ₃ (NBu ₂ ) ₃ ]Cl -28.0 41 303 - 674.3

(19) [C ₃ (NBu ₂ ) ₃ ]TFSA -74.5 6.7 400 230.4 38.3

(20) [C ₃ (NBu ₂ ) ₃ ]Br -32 n.o. 318

(21) [C ₃ (NBu ₂ ) ₃ ]DCA -61.8 17.3 335 292.8 41

(22) [C ₃ (NBu ₂ ) ₃ ]N0 ₃ -61.7 n.o. 234 - 149.6

(23) [C ₃ (NBu ₂ ) ₃ ]BF ₄ -50.9 33.5 373 - 89.9

(24) [C ₃ (NBu ₂ ) ₃ ]OTf -58.3 44.5 388 - 24.9

(25) [C ₃ (N(CH ₂ CH ₂ OH) ₂ ) ₃ ]Cl -41.7 n.o. 227

(26) [C ₃ (N(CH ₂ CH ₂ OH) ₂ ) ₃ ]F 158

(29) [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]TFSA -81.5 8.8 306 125.7 21.1

(30) [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]DCA -67.8 23.7 270 210.5 27.2

(31) [C ₃ (NBuMe) ₃ ]Cl n.o. 87.9 293 - -

(32) [C ₃ (NBuMe) ₃ ]TFSA -81.4 n.o. 386 104.4 19.4

(33) [C ₃ (NBuMe) ₃ ]DCA -72.9 n.o. 338 101.2 16.9

(34) [C ₃ (NBuMe) ₃ ]N0 ₃ -55 24 315 - 68.3

(35) [C ₃ (NBuMe) ₃ ]BF ₄ -61.5 n.o. 374 659 22.1

(36) [C ₃ (NBuMe) ₃ ]SCN -69 n.o. 313 279.9 30.9

(37) [C ₃ (NStMe) ₃ ]Cl n.o. 51.7 278 Compound T T _d Viscosity Viscosity

(°C) ^a (°C)° (°C)* (mPa.s (mPa.s at at 20°C) 60°C)

(38) [C ₃ (NStMe) ₃ ]TFSA n.o. 64.7 384

(39) [C ₃ (NStMe) ₃ ]DCA n.o. 52.3 279

(41) [C ₃ (NEt ₂ ) ₂ (NMe ₂ )]TFSA n.o. 17.0 379 83.6 17.9

(42) [C ₃ (NEt ₂ )2(NMe ₂ )]DCA -85 32.1 322 58.4 13.2

(44) [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]TFSA -85.9 -4.3 403 125.7 23.1

(45) [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]DCA -81.8 30.2 334 105 19.4

(47) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]TFSA -81.4 n.o. 396 182.1 30.2

(48) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]DCA -79.8 n.o. 348 131 22.2

(50) [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]TFSA -62.1 n.o.

(51) [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]F 174

(54) [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CHCH ₂ ) ₂ )]TFSA -87.3 -26.4 358 111.4 20.9

(56) [C ₃ (NEt ₂ ) ₂ (NBuMe)]TFSA -88.2 n.o. 384 106.2 21.1

(57) [C ₃ (NEt ₂ ) ₂ (NBuMe)]DCA -83 8.1 332 73.7 15.3

(59) [C ₃ (NEt ₂ ) ₂ (NHexMe)]TFSA -84 n.o. 396 82.1 16.7

(60) [C ₃ (NEt ₂ ) ₂ (NHexMe)]DCA -82 n.o. 348 69 14.3

(61) [C ₃ (NEt ₂ ) ₂ (NHBu)]MeS0 ₄ -67.9 n.o. 242 344.3 45

(62) [C ₃ (NEt ₂ ) ₂ (NHBu)]TFSA -80.1 n.o. 301 175.7 25.5

(63) [C ₃ (NEt ₂ ) ₂ (NHBu)]DCA -69.7 n.o. 233 251.3 31.6

(64) [C ₃ (NEt ₂ ) ₂ (NH((S)-CHMeCOOH))]MeS0 ₄ -7.9 n.o. 214 - 1006 (65°C)

(65) [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]Cl n.o. 118 292 - -

(68) [C ₃ (NPent ₂ ) ₃ ]TFSA -73 4 395 268.7 41.9

(69) [C ₃ (NPent ₂ ) ₃ ]DCA -64 n.o. 321 307.5 40.0

(70) [C ₃ (NHex ₂ ) ₃ ]Cl -53.7 n.o.

(71) [C ₃ (NHex ₂ ) ₃ ]TFSA -70.6 3.1 406 273.0 44.9

(72) [C ₃ (NHex ₂ ) ₃ ]DCA -64.1 n.o. 321 332.3 46.9 Compound T Viscosity Viscosity

(°C)" (°C)" (°C)* (mPa.s (mPa.s at at 20°C) 60°C)

(74) [C ₃ (NDec ₂ ) ₃ ]TFSA n.o. 8 401 407.6 56.0

(75) [C ₃ (NDec ₂ ) ₃ ]DCA n.o. -13 321 553.7 62.3

(76) [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]TFSA n.o. 51.8 342

(77) [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]DCA -52.3 46.7 332

(79) [C ₃ (NEt ₂ ) ₂ (NHHex)]TFSA -82 n.o. 371 170.6 27.9

(80) [C ₃ (NEt ₂ ) ₂ (NH ₂ )]MeS0 ₄ 230 - -

(81) [C ₃ (NEt ₂ ) ₂ (NH ₂ )]TFSA 334 - -

(82) [C ₃ (NPhH) ₃ ]TFSA 16.7 149 295 - -

(83) [C ₃ (NEt ₂ ) ₂ (NHBu)]BF ₄ 228

(84) [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]I 74.0 319 - -

(85) [C ₃ (NEt ₂ ) ₃ ]I 46.2 299 - -

(86) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]I 292 - 127

(87) [C ₃ (NMe ₂ ) ₃ ]DCA 1 17 285 - -

(88) [C ₃ (NMe ₂ ) ₃ ]SCN 148 270 - -

(89) [C ₃ (NBu ₂ ) ₃ ]B(CN) ₄ 275 187 27

(90) [C ₃ (NBu ₂ ) ₃ ]FAP 303 334 41

(91) [C ₃ (NHex ₂ ) ₃ ](BuO) ₂ P0 ₂ 232 227 30.2

(92) [C ₃ (NEt ₂ ) ₂ (NH((S)-CHMeCOOH))]TFSA -30.1 n.o. 253 - 838 (75°C)

(93) [C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]MeS0 ₄ -15.7 n.o. 228 - 834 (75°C)

(94) [C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]TFSA -22.2 n.o. 275 - 564

(95) [C ₃ (NEt ₂ ) ₂ (NH(C4H ₈ COOH))]MeS0 ₄ -50.4 20.9 214 - -

(96) [C ₃ (NEt ₂ ) ₂ (NH(C ₄ H ₈ COOH))]TFSA -40.7 n.o. 247 - 791 (70°C)

(97) [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₅ OHCOOH))]MeS0 ₄ n.o. 43.6 197 - -

(98) [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₅ OHCOOH))]TFSA -22.1 n.o. 176 - 884 (75°C)

(99) [C ₃ (NBu ₂ ) ₃ ]NCO 236 397 Compound T Viscosity Viscosity

( ⁰ C)" (°C) ^e (°C)* (mPa.s (mPa.s at at 20°C) 60°C)

(100) [C ₃ (NBu ₂ ) ₃ ]SnCl3 -44.4 n.o. 279

(101) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]OTf 314 ^• 444 54.7

(103) [C ₃ (NEt ₂ ) ₂ (N(i-Pr) ₂ )]DCA 289 164.5 24.9

(105) [C ₃ (NMe ₂ ) ₂ (NHexMe)]TFSA 295 65.9 13.0

(106) [C ₃ (NMe ₂ ) ₂ (NHex ₂ )]TFSA 335 162.4 22.5

(107) [C ₃ (NMe ₂ ) ₂ (NBu ₂ )]TFSA 297 53.1 9.6 ^a Determined by DSC at 10 °C/min. * Determined by TGA at 10 °C/min. ⁰ Also a solid-solid transition at 66.0 °C. n.o. = not observed.

Table 2: Microanalytical data

Compound C H N CI F S

(1) [C ₃ (NMe ₂ ) ₃ ]Cl 46.49 9.19 18.07

46.92 9.47 16.49

(2) [C ₃ (NMe ₂ ) ₃ ]TFSA 29.46 4.05 12.49

29.58 4.10 12.28

(3) [C,(NEt ₂ ) ₃ ]C1.1.6H ₂ 0 56.89 10.57 13.27 11.19

56.96 10.12 12.66 11.93

(4) [C ₃ (NEt ₂ ) ₃ ]TFSA 38.34 5.68 10.52

38.80 5.81 10.60

(5) [C ₃ (NEt ₂ ) ₃ ]DCA 64.12 9.50 26.39

63.99 9.77 26.59

(6) [C ₃ (NEt ₂ ) ₃ ]NO ₃ .0.5H ₂ O 55.70 9.66 17.32

55.63 9.80 17.41

(7) [C ₃ (NEt ₂ ) ₃ ]BF ₄ 53.11 8.91 12.39

52.91 9.10 12.36

(8) [C ₃ (NEt ₂ ) ₃ ]SCN.0.24H ₂ O 61.05 9.76 17.80

61.08 9.99 17.82 Compound C H N CI F S

(9) [C ₃ (NEt ₂ ) ₃ ][p-MeC ₆ H ₄ S0 ₃ ] 61.72 8.82 9.81

61.73 9.23 9.83

(10) [C ₃ (NEt ₂ ) ₃ ]OTf 47.87 7.53 10.47

48.03 7.65 10.44

(l l) [C ₃ (NPr ₂ ) ₃ ]C1.2H ₂ 0 61.81 11.36 10.30 8.69

62.01 10.77 8.93 9.56

(12) [C ₃ (NPr ₂ ) ₃ ]TFSA 44.79 6.86 9.08

44.95 6.99 9.11

(13) [C ₃ (NPr ₂ ) ₃ ]DCA.0.6H ₂ O 66.82 10.53 20.33

67.19 10.57 19.77

(14) [C ₃ (NPr ₂ ) ₃ ]F.2EtOH.2H ₂ 0 62.07 12.08 8.69

61.95 12.48 8.77

(16) [C ₃ (NPr ₂ ) ₃ ]N0 ₃ .1.4H ₂ 0 59.62 10.65 13.24

59.80 10.76 13.10

(17) [C ₃ (NPr ₂ ) ₃ ]BF ₄ 59.57 10.00 9.92

59.85 10.25 10.05

(18) [C ₃ (NBu ₂ ) ₃ ]C1.0.72H ₂ O 69.12 11.91 8.96 7.55

69.09 11.38 9.06 7.99

(19) [C ₃ (NBu ₂ ) ₃ ]TFSA 49.70 7.77 7.99

49.43 7.92 8.07

(20) [C ₃ (NBu ₂ ) ₃ ]Br.l.35H ₂ 0 61.77 10.89 8.00

61.82 10.37 7.63

(21) [C ₃ (NBu ₂ ) ₃ ]DCA.0.4H ₂ O 70.51 11.18 17.01

70.31 11.20 17.28

(22) [C ₃ (NBu ₂ ) ₃ ]NO ₃ .0.6H ₂ O 65.71 11.27 11.35

65.49 11.42 11.80

(23) [C ₃ (NBu ₂ ) ₃ ]BF ₄ 63.89 10.72 8.28

63.88 10.50 8.14

(24) [C ₃ (NBu ₂ ) ₃ ]OTf 59.02 9.55 7.37

59.33 9.83 7.41 Compound C H N CI F S

(26) [C ₃ (N(CH ₂ CH ₂ OH) ₂ ) ₃ ]F.0.16H ₂ O 48.65 8.25 11.34

48.73 8.07 11.05

(27) [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]C1.0.9H ₂ O 67.05 8.52 11.17 9.43

67. 22 8.51 10.82 9.17

(28) [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]Br .0.41 H ₂ 0 61.25 7.54 10.20

61.47 7.58 9.81

(29) [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]TFSA 45.68 5.00 9.27

45.95 5.22 9.56

(30) [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]DCA.0.5H ₂ O 69.14 7.82 21.03

69.11 7.71 21.06

(31) [C ₃ (NBuMe) ₃ ]C1.1.24H ₂ 0 61.37 10.87 11.93

61.32 10.94 11.99

(32) [C ₃ (NBuMe) ₃ ]TFSA 41.80 6.31 9.75

41.52 6.30 9.88

(33) [C ₃ (NBuMe) ₃ ]DCA 66.63 10.06 23.31

66.38 10.22 23.39

(34) [C ₃ (NBuMe) ₃ ]NO ₃ .0.45H ₂ O 59.29 10.20 15.36

59.29 10.33 15.49

(35) [C ₃ (NBuMe) ₃ ]BF ₄ 0.19H ₂ O 56.20 9.53 10.92

56.18 9.36 11.00

(36) [C ₃ (NBuMe) ₃ ]SCN.0.33H ₂ O 63.66 10.31 15.63

63.66 10.37 15.73

(37) [C ₃ (NStMe) ₃ ]C1.2.2H ₂ 0 75.17 13.08 4.38

75.18 12.86 4.56

(38) [C ₃ (NStMe) ₃ ]TFSA.1.5H ₂ 0 62.54 10.41 4.71

62.54 10.24 4.87

(39) [C ₃ (NStMe) ₃ ]DCA.0.7H ₂ O 77.39 12.72 8.73

77.31 12.90 9.10

(41) [C ₃ (NEt ₂ ) ₂ (NMe ₂ )]TFSA 35.71 5.19 11.11

36.38 5.48 11.13 Compound C H N CI F S

(42) [C ₃ (NEt ₂ ) ₂ (NMe ₂ )]DCA.lH ₂ 0 58.41 9.15 27.25

58.91 8.90 26.66

(44) [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]TFSA 42.85 6.51 9.52 19.36 10.89

42.95 6.72 9.60 19.42 10.79

(45) [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]DCA 67.34 10.23 22.44

64.93 9.68 21.85

(47) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]TFSA 46.57 7.19 8.69 17.68

47.35 7.58 8.78 14.87

(48) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]DCA.0.85H ₂ O 67.33 10.78 18.84

67.43 10.62 18.71

(54) [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CHCH ₂ ) ₂ )]TFSA 41.00 5.43 10.07

41.03 5.47 10.04

(56) [C ₃ (NEt ₂ ) ₂ (NBuMe)]TFSA 39.55 5.90 10.25 20.85

40.41 5.87 10.28 17.08

(57) [C ₃ (NEt ₂ ) ₂ (NBuMe)]DCA.0.5H ₂ O 63.31 9.74 24.61

63.08 9.86 24.78

(59) [C ₃ (NEt ₂ ) ₂ (NHexMe)]TFSA 41.80 6.31 9.75 19.84 11.16

42.78 6.35 9.75 17.29 10.07

(60) [C ₃ (NEt ₂ ) ₂ (NHexMe)]DCA 66.63 10.06 23.31

64.61 9.95 21.89

(61) [C ₃ (NEt ₂ ) ₂ ( HBu)]MeS0 ₄ 52.87 9.15 11.56

52.27 9.25 11.49

(62) [C ₃ (NEt ₂ ) ₂ (NHBu)]TFSA 64.12 9.50 26.40

63.91 9.93 25.96

(63) [C ₃ (NEt ₂ ) ₂ (NHBu)]DCA 64.12 9.50 25.96

63.91 9.93 25.96

(64) [C ₃ (NEt ₂ ) ₂ (NH((5)-CHMeCOOH))]MeS0 ₄ 51.33 8.13 12.23

(25% zwitterion) 51.70 8.34 11.82

(65) [C ₃ (Ni-Pr ₂ ) ₂ (NBu ₂ )]C1.0.4H ₂ O 67.83 11.58 10.32

67.83 11.48 10.50 Compound C H N CI F S

(67) [C ₃ (NPent ₂ ) ₃ ]Cl.l.lH ₂ 0 70.76 12.27 7.50

70.76 12.22 7.65

(68) [C ₃ (NPent ₂ ) ₃ ]TFSA 53.55 8.47 7.14

54.43 8.57 7.23

(69) [C ₃ (NPent ₂ ) ₃ ]DCA.0.16H ₂ O 73.26 11.65 14.65

73.26 11.58 14.64

(71) [C ₃ (NHex ₂ ) ₃ ]TFSA 56.66 9.04 6.45

57.30 9.22 6.48

(72) [C ₃ (NHex ₂ ) ₃ ]DCA 75.17 12.00 12.83

75.31 12.25 12.72

(73) [C ₃ (NDec ₂ ) ₃ ]C1.0.59H ₂ O 77.86 13.19 4.32

77.86 13.23 4.43

(74) [C ₃ (NDec ₂ ) ₃ ]TFSA 64.74 10.53 4.65

64.80 10.57 4.84

(75) [C ₃ (NDec ₂ ) ₃ ]DCA 78.72 12.81 8.47

78.61 12.88 8.51

(76) [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]TFSA 46.57 7.19 8.69

(4.4% [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]Cl) 47.23 7.26 8.62

(77) [C ₃ (N(i-Pr) ₂ ) ₂ (NBu ₂ )]DCA 69.72 10.77 19.51

69.67 10.76 19.64

(79) [C ₃ (NEt ₂ ) ₂ (NHHex)]TFSA 40.71 6.11 9.99

41.43 6.26 10.07

(80) [C ₃ (NEt ₂ ) ₂ (NH ₂ )]MeS0 ₄ .1.5H ₂ 0 43.10 8.43 12.56

42.78 8.29 12.84

(81) [C ₃ (NEt ₂ ) ₂ (NH ₂ )]TFSA 34.51 4.87 11.86

(4% cyclopropenone) 34.15 4.94 11.89

(82) [C ₃ (NPhH) ₃ ]TFSA 46.62 3.06 9.45

46.66 3.21 9.35

(83) [C ₃ (NEt ₂ ) ₂ (NHBu)]BF ₄ .0.25H ₂ O 52.31 9.23 12.22

52.41 8.94 12.22 Compound C H N CI F S

(84) [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]I 52.41 8.97 9.65

52.87 8.95 9.65

(85) [C ₃ (NEt ₂ ) ₃ ]I 47.49 7.97 11.07

48.44 8.35 10.72

(86) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]I.0.25H ₂ O 55.69 9.44 8.47

55.62 9.53 8.52

(87) [C ₃ (NMe ₂ ) ₃ ]DCA 55.89 7.92 33.58

(15% [C ₃ (NMe ₂ ) ₃ ]Cl) 55.64 7.93 33.63

(88) [C ₃ ( Me ₂ ) ₃ ]SCN 53.07 8.15 24.13

53.87 8.29 23.40

(89) [C ₃ (NBu ₂ ) ₃ ]B(CN) ₄ 69.51 10.16 18.30

69.75 10.30 18.48

(90) [C ₃ (NBu ₂ ) ₃ ]FAP 45.79 6.28 4.85

46.72 6.48 4.77

(91) [C ₃ (NHex ₂ ) ₃ ](BuO) ₂ PO ₂ .0.5H ₂ O 69.84 12.22 5.20

69.50 12.27 5.26

(92) [C ₃ (NEt ₂ ) ₂ (NH((S)-CHMeCOOH))]TFSA 36.15 4.96 10.43

(4% zwitterion) 36.14 5.31 10.40

(93) [C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]MeS0 ₄ 54.47 8.38 11.52

(38% zwitterions, 3% water) 54.57 8.89 11.59

(94) [C ₃ (NEt ₂ ) ₂ (N(C ₄ H ₇ COOH))]TFSA 40.59 5.73 10.13

(15% zwitterions, 3% water) 40.41 5.69 10.24

(95) [C ₃ (NEt ₂ ) ₂ (NH(C ₄ H ₈ COOH))]MeS0 ₄ 57.01 9.05 12.15

(50% zwitterion, 1% water) 57.10 9.01 12.08

(96) [C ₃ (NEt ₂ ) ₂ (NH(C ₄ H ₈ COOH))]TFSA 41.49 6.27 10.27

(19% zwitterion, 3% water) 41.38 6.46 10.56

(97) [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₆ OCOOH))]MeS0 ₄ 54.44 8.47 12.39

(55% zwitterion) 54.43 8.46 12.38

(98) [C ₃ (NEt ₂ ) ₂ (NH(C ₃ H ₆ OCOOH))]TFSA 38.51 5.39 10.36

(8% zwitterion) 38.57 5.51 10.52 Compound C H N CI Γ s

(99) [C ₃ (NBu ₂ ) ₃ ]NC0.2.4H ₂ 0 66.46 11.71 1 1.07

66.85 1 1.68 10.67

(100) [C ₃ (NBu ₂ )3][SnCl ₃ ].0.2H ₂ O 49.94 8.44 6.47

49.97 8.57 6.48

(103) [C ₃ (NEt ₂ ) ₂ (N(i-Pr) ₂ )]DCA.0.35H ₂ O 64.68 9.91 23.82

64.35 9.81 24.12

Table 3: Conductivity data

Conductivity (mS/cm)

Compound

20 °C 30 °C 40 °C 50 °C 60 °C 70 °C 80 °C 90 °C

(4) [C ₃ (NEt ₂ ) ₃ ]TFSA 1.387 1.983 2.755 3.681 4.752 5.972 7.349 8.857

(5) [C ₃ (NEt ₂ ) ₃ ]DCA 4.688 6.797 9.199 11.97 15.14 18.63 22.40 26.33

(9) [C ₃ ( Et ₂ ) ₃ ][ -MeC ₆ H ₄ S0 ₃ ] 0.090 0.217 0.446 0.828 1.394 2.180 3.220 4.51

(12) [C ₃ (NPr ₂ ) ₃ ]TFSA 0.498 0.862 1.323 1.904 2.629 3.491 4.498 5.642

(13) [C ₃ (NPr ₂ ) ₃ ]DCA 0.634 5.871 8.016 10.481 13.246

(16) [C ₃ ( Pr ₂ ) ₃ ]N0 ₃ 0.069 0.181 0.365 0.678 1.060 1.352 1.944 2.664

(18) [C ₃ (NBu ₂ ) ₃ ]Cl 0.014 0.035 0.081 0.164 0.306 0.528 0.857

(19) [C ₃ (NBu ₂ ) ₃ ]TFSA 0.428 0.694 1.057 1.535 2.144 2.915 3.819 4.870

(21) [C ₃ ( Bu ₂ ) ₃ ]DCA 1.158 1.892 2.886 4.161 5.732 7.576 9.684

(22) [C ₃ (NBu ₂ ) ₃ ]N0 ₃ 0.071 0.161 0.323 0.590 0.965 1.567 2.340

(23) [C ₃ (NBu ₂ ) ₃ ]BF ₄ 0.084 0.173 0.315 0.532 0.841 1.262 1.795 2.453

(24) [C ₃ (NBu ₂ ) ₃ ]OTf 0.299 0.531 0.868 1.342 1.965 2.749 3.714

(29) [C ₃ ( (CH ₂ CHCH ₂ ) ₂ ) ₃ ]TFSA 0.927 1.472 2.192 3.099 4.164 5.424 6.826 8.397

(30) [C ₃ (N(CH ₂ CHCH ₂ ) ₂ ) ₃ ]DCA 0.879 1.562 2.525 3.818 5.424 7.349 9.235

(32) [C ₃ (NBuMe) ₃ ]TFSA 0.939 1.451 2.074 2.825 3.711 4.723 5.869 7.124

(33) [C ₃ (NBuMe) ₃ ]DCA 2.160 3.507 5.445

(35) [C ₃ (NBuMe) ₃ ]BF ₄ 0.252 0.529 0.928 1.492 2.252 3.196 4.363 5.691

(41) [C ₃ (NEt ₂ ) ₂ (NMe ₂ )TFSA 1.572 2.250 3.101 4.106 5.264 6.547 7.933 9.374

(42) [C ₃ (NEt ₂ ) ₂ (NMe ₂ )DCA 4.643 6.969 9.537 12.44 15.70 19.25 23.13 27.21 Conductivity (mS/cm)

Compound

20 °C 30 °C 40 °C 50 °C 60 °C 70 °C 80 °C 90 °C

(44) [C ₃ (NEt ₂ ) ₂ (NBu ₂ )]TFSA 0.850 1.288 1.847 2.532 3.346 4.284 5.348 6.522

(45) [C ₃ (NEt ₂ )2(NBu ₂ )]DCA 2.203 3.424 4.912 6.703 8.794 11.16 13.82 16.71

(48) [C ₃ (NEt ₂ ) ₂ (NHex ₂ )]DCA 1.028 1.710 2.572 3.641 4.939 6.463 8.210 10.164

(50) [C ₃ (NEt ₂ ) ₂ (N(CH ₂ CH ₂ OH) ₂ )]TFSA 0.168 0.317 0.545 0.873 1.311 1.844 2.498 3.283

(56) [C ₃ (NEt ₂ ) ₂ (NBuMe)TFSA 1.225 1.839 2.512 3.346 4.322 5.413 6.630 7.964

(57) [C ₃ (NEt ₂ ) ₂ (NBuMe)DCA 3.501 5.119 7.134 9.503 12.20 15.24 18.60 22.16

(59) [C ₃ (NEt ₂ ) ₂ (NHexMe)TFSA 1.176 1.818 2.650 3.690 4.940 6.380 8.030

(60) [C ₃ (NEt ₂ ) ₂ (NHexMe)DCA 2.770 4.340 6.340 8.820 11.75 15.13 18.88

(68) [C ₃ (NPent ₂ ) ₃ ]TFSA 0.245 0.420 0.670 1.011 1.453 2.000 2.670 3.450

(69) [C ₃ (NPent ₂ ) ₃ ]DCA 0.295 0.543 0.914 1.439 2.140 3.030 4.120 5.400

(71) [C ₃ (NHex ₂ ) ₃ ]TFSA 0.141 0.226 0.349 0.508 0.710 0.965 1.257 1.602

(72) [C ₃ (NHex ₂ ) ₃ ]DCA 0.161 0.260 0.414 0.620 0.891 1.228 1.644 2.129

(74) [C ₃ (NDec ₂ ) ₃ ]TFSA 0.027 0.048 0.082 0.131 0.198 0.288 0.404

(75) [C ₃ (NDec ₂ ) ₃ ]DCA 0.022 0.043 0.078 0.130 0.205 0.307 0.440

Reaction using triaminocyclopropenium salt as a solvent

Sodium /3-naphthoxide (0.210 g, 1.26 mmol) was dissolved in [C ₃ (NBu ₂ )3]BF ₄ (1.71 g, 3.3 mmol) over 1 h. Benzyl chloride (0.160 g, 1.25 mmol) was added and the solution stirred at 25 °C for 24 h. Addition of 10 mL of 1 :2 water:ethanol dissolved the [C ₃ (NBu ₂ )3]BF ₄ and precipitated the organic products. The organic products were then analysed by Ή NMR to determine the ratio of O-alkylation: C-alkylation.

In order to investigate potential solvent effects using triaminocyclopropenium salts as ionic liquids, a benzylation of sodium- 3-napthoxide was carried out in [C ₃ (NBu ₂ )3]BF ₄ . In phosphonium, ammonium and imidazolium ionic liquids, 92-99% O-alkylation occurs (M. Badri, J. J. Brunet and R. Perron, Tetrahedron Lett., 1992, 33, 4435, which is incorporated herein in its entirety by reference). Using similar conditions with [C ₃ (NBu ₂ )3]BF ₄ , no products of C-alkylation were able to be observed. This illustrates that triaminocyclopropenium salts have similar polar solvent effects to conventional ionic liquids. It is not the intention to limit the scope of the invention to the abovementioned examples only. As would be appreciated by a skilled person in the art, many variations are possible without departing from the scope of the invention as set out in the accompanying claims.

In addition, where features or aspects of the invention are described in terms of a Markush group, those skilled in the art will recognise that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group.