SYNTHESIS AND CHARACTERIZATION OF METATHESIS CATALYSTS

RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62/484,686, filed April 12, 2017, the contents of which are incorporated herein by reference.

TECHNICAL FIELD

[0002] This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.

BACKGROUND

[0003] Since its discovery in the 1950s, olefin metathesis has emerged as a valuable synthetic method for the formation of carbon-carbon double bonds. Recent advances in applications to organic syntheses and polymer syntheses mostly rely on developments of well-defined olefin metathesis catalysts.

[0004] The technology of ruthenium metathesis catalysts has enabled the development of several research platforms including: ring opening metathesis polymerization (ROMP), ring opening cross metathesis (ROCM), cross metathesis (CM), ring closing metathesis (RCM).

[0005] First Generation Grubbs ruthenium olefin metathesis catalysts, such as:

(PCy3)2(CI)2Ru=CHPh, have been largely used in organic synthesis.

[0006] The incorporation of certain types of N-Heterocyclic Carbene (NHC) ligands played an essential role in the development of ruthenium metathesis catalysts, giving rise to the Second Generation Grubbs ruthenium olefin metathesis catalysts, such as:

(IMesH2)(PCy3) (CI)2Ru=CHPh, where IMesh is 1 ,3-dimesityl-4,5-dihydroimidazol-2- ylidene.

[0007] In order to exchange the phosphine on the Second Generation Grubbs ruthenium olefin metathesis catalysts, the Grubbs group reported in 2001 (Organometallics 2001 , 20, 5314-5318) a method involving a precursor bearing two pyridine ligands: (IMesH2)(CI)2(C5H5N)2Ru =CHPh. The labile pyridine ligands have allowed the preparation of diverse ruthenium olefin metathesis catalysts. However, the preparation of pyridine complexes, requires large quantities of expensive and malodorous reagents (pyridine), and difficult reaction conditions (negative °C temperatures) especially for industrial scale-up.

[0008] Therefore, there is an ongoing need for efficient, high yield, high purity and ease in scaling up procedures for the synthesis of olefin metathesis catalysts, particularly Second Generation Grubbs ruthenium olefin metathesis catalysts.

SUMMARY OF THE INVENTION

[0009] To meet this need the inventors have discovered novel ruthenium olefin metathesis catalysts, bearing a thiourea ligand as described herein. The ruthenium olefin metathesis catalysts bearing stable thiourea ligands and long shelf life.

[00010] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula I):

Formula (I)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L ¹ and L ² are independently neutral electron donor ligands;

n is 0 or 1 ; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0; R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to; X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X ¹ and X ² are independently chlorine, bromine, iodine or fluorine;

R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R ¹ is hydrogen, and R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene.

[00011] In one embodiment, the invention provides a method of synthesizing the olefin metathesis catalysts of the invention.

[00012] In one embodiment, the invention provides a method of using the olefin metathesis catalysts of the invention in metathesis reactions.

[00013] In one embodiment, the invention provides a method of synthesizing a Second Generation Grubbs catalyst, using an olefin metathesis catalyst of the invention.

[00014] Other embodiments of the invention are described herein.

[00015] These and other aspects of the present invention will be apparent to one of skill in the art, in light of the following detailed description and examples. Furthermore, it is to be understood that none of the embodiments or examples of the invention described herein are to be interpreted as being limiting.

BRI EF DESCRI PTION OF TH E FIGU RES

[00016] Figure 1 depicts an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C801 TU.

[00017] Figure 2 depicts the reactivity in ring closing metathesis of diethyl diallylmalonate in the presence of olefin metathesis catalysts of the invention.

DETAI LED DESCRI PTION

[00018] Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting.

[00019] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an olefin" includes a single olefin as well as a combination or mixture of two or more olefins, reference to "a substituent" encompasses a single substituent as well as two or more substituents, and the like.

[00020] As used in the specification and the appended claims, the terms "for example," "for instance," "such as," or "including" are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention and are not meant to be limiting in any fashion.

[00021] In this specification and in the claims that follow, reference will be made to a number of terms, which are defined herein.

[00022] The term "alkyl" as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to 30 carbon atoms, generally containing 1 to 24 carbon atoms, typically 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, /so-propyl, n-butyl, /so-butyl, f-butyl, octyl, decyl, and the like, as well as cycloalkyi groups such as cyclopentyl, cyclohexyl and the like. The term "lower alkyl" intends an alkyl group of 1 to 6 carbon atoms, and the specific term "cycloalkyi" intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms. The term "substituted alkyl" refers to alkyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms "alkyl" and "lower alkyl" include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.

[00023] The term "alkylene" as used herein refers to a divalent linear, branched, or cyclic alkyl group, where "alkyl" is as defined above.

[00024] The term "alkenyl" as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to 30 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, /so-propenyl, n-butenyl, /so-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Generally, "alkenyl" groups herein contain 2 to 24 carbon atoms, typically "alkenyl" groups herein contain 2 to 12 carbon atoms. The term "lower alkenyl" intends an "alkenyl" group of 2 to 6 carbon atoms, and the specific term "cycloalkenyl" intends a cyclic "alkenyl" group, typically having 5 to 8 carbon atoms. The term "substituted alkenyl" refers to "alkenyl" substituted with one or more substituent groups, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" refer to "alkenyl" in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms "alkenyl" and "lower alkenyl" include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing "alkenyl" and lower "alkenyl," respectively. The term "alkenyl" is used interchangeably with the term "olefin" herein.

[00025] The term "alkenylene" as used herein refers to a divalent linear, branched, or cyclic alkenyl group, where "alkenyl" is as defined above.

[00026] The term "alkynyl" as used herein refers to a linear or branched hydrocarbon group of 2 to 30 carbon atoms containing at least one triple bond, such as ethynyl, n- propynyl, and the like. Generally, "alkynyl" groups herein contain 2 to 24 carbon atoms; typical "alkynyl" groups described herein contain 2 to 12 carbon atoms. The term "lower alkynyl" intends an "alkynyl" group of 2 to 6 carbon atoms. The term "substituted alkynyl" refers to "alkynyl" substituted with one or more substituent groups, and the terms "heteroatom-containing alkynyl" and "heteroalkynyl" refer to "alkynyl" in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms "alkynyl" and "lower alkynyl" include linear, branched, unsubstituted, substituted, and/or heteroatom-containing "alkynyl" and lower "alkynyl" respectively.

[00027] The term "alkoxy" as used herein refers to an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy" group can be represented as -O-alkyl where alkyl is as defined above. A "lower alkoxy" group intends an alkoxy group containing 1 to 6 carbon atoms. Analogously, "alkenyloxy" and "lower alkenyloxy" respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and "alkynyloxy" and "lower alkynyloxy" respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage. [00028] The term "aryl" as used herein, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). "Aryl" groups contain 5 to 30 carbon atoms, generally "aryl" groups contain 5 to 20 carbon atoms; and typically, "aryl" groups contain 5 to 14 carbon atoms. Exemplary "aryl" groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. "Substituted aryl" refers to an aryl moiety substituted with one or more substituent groups; for example 2,4,6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl, 2,6-di-/so-propylphenyl (i.e., DIPP or DiPP), 2-/so-propyl-phenyl (i.e., IPP, Ipp or ipp), 2-/so-propyl-6-methylphenyl (i.e., MIPP or Mipp or MiPP). The terms "heteroatom-containing aryl" and "heteroaryl" refer to "aryl" substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.

[00029] The term "aryloxy" as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein "aryl" is as defined above. An "aryloxy" group can be represented as -O-aryl where aryl is as defined above. Preferred "aryloxy" groups contain 5 to 24 carbon atoms, and particularly preferred "aryloxy" groups contain 5 to 14 carbon atoms. Examples of "aryloxy" groups include, without limitation, phenoxy, o-halo- phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

[00030] The term "alkaryl" refers to an aryl group with an alkyl substituent, and the term "aralkyl" refers to an alkyl group with an aryl substituent, wherein "aryl" and "alkyl" are as defined above. "Alkaryl" and "aralkyl" groups contain 6 to 30 carbon atoms; generally, "alkaryl" and "aralkyl" groups contain 6 to 20 carbon atoms; and typically, "alkaryl" and "aralkyl" groups contain 6 to 16 carbon atoms. "Alkaryl" groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1 ,4-diene, and the like. Examples of "aralkyl" groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4- benzylcyclohexylmethyl, and the like. The terms "alkaryloxy" and "aralkyloxy" refer to substituents of the formula -OR wherein R is "alkaryl" or "aralkyl," respectively, as defined herein.

[00031] The term "acyl" refers to substituents having the formula -(CO)-alkyl, -(CO)- aryl, or -(CO)-aralkyl, and the term "acyloxy" refers to substituents having the formula -O(CO)-alkyl, -O(CO)-aryl, or -O(CO)-aralkyl, wherein "alkyl," "aryl," and "aralkyl" are as defined above.

[00032] The terms "cyclic" and "ring" refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom-containing, and that can be monocyclic, bicyclic, or polycyclic. The term "alicyclic" is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and can be monocyclic, bicyclic, or polycyclic.

[00033] The terms "halo," "halogen" and "halide" are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

[00034] The term "hydrocarbyl" refers to univalent "hydrocarbyl" moieties containing 1 to 30 carbon atoms, typically containing 1 to 24 carbon atoms, specifically containing 1 to 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term "lower hydrocarbyl" intends a "hydrocarbyl" group of 1 to 6 carbon atoms, typically 1 to 4 carbon atoms, and the term "hydrocarbylene" intends a divalent "hydrocarbyl" moiety containing 1 to 30 carbon atoms, typically 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term "lower hydrocarbylene" intends a "hydrocarbylene" group of 1 to 6 carbon atoms. "Substituted hydrocarbyl" refers to "hydrocarbyl" substituted with one or more substituent groups, and the terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, "substituted hydrocarbylene" refers to "hydrocarbylene" substituted with one or more substituent groups, and the terms "heteroatom-containing hydrocarbylene" and "heterohydrocarbylene" refer to "hydrocarbylene" in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term "hydrocarbyl" and "hydrocarbylene" are to be interpreted as including substituted and/or heteroatom- containing "hydrocarbyl" and "hydrocarbylene" moieties, respectively. [00035] The term "heteroatom-containing" as in a "heteroatom-containing hydrocarbyl group" refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. Similarly, the term "heteroalkyl" refers to an alkyl substituent that is heteroatom- containing, the term "heterocyclic" refers to a cyclic substituent that is heteroatom- containing, the terms "heteroaryl" and "heteroaromatic" respectively refer to "aryl" and "aromatic" substituents that are heteroatom-containing, and the like. It should be noted that a "heterocyclic" group or compound may or may not be aromatic, and further that "heterocycles" can be monocyclic, bicyclic, or polycyclic as described above with respect to the term "aryl." Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl- substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1 ,2,4-triazolyl, tetrazolyl, etc.

[00036] By "substituted" as in "substituted hydrocarbyl," "substituted alkyl," "substituted aryl," and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation hydrocarbyl groups, as defined herein, as well as functional groups ("Fn"), such as halo, hydroxyl, sulfhydryl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and C6-C24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C24 alkylcarbonyloxy (-O-CO- alkyl) and C6-C24 arylcarbonyloxy (-O-CO-aryl)), C2-C24 alkoxycarbonyl (-(CO)-O-alkyl), C6-C24 aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X where X is halo), C2-C24 alkylcarbonato (-O-(CO)-O-alkyl), C6-C24 arylcarbonato (-O-(CO)-O-aryl), carboxy (- COOH), carboxylato (-COO ^" ), carbamoyl (-(CO)-NH ₂ ), mono-(Ci-C24 alkyl)-substituted carbamoyl (-(CO)-NH(Ci-C24 alkyl)), di-(Ci-C24 alkyl)-substituted carbamoyl (-(CO)-N(Ci- C24 alkyl)2), mono-(Ci-C24 haloalkyl)-substituted carbamoyl (-(CO)-NH(Ci-C24 alkyl)), di- (C1-C24 haloalkyl)-substituted carbamoyl (-(CO)-N(Ci-C24 alkyl)2), mono-(C5-C24 aryl)- substituted carbamoyl (-(CO)-NH-aryl), di-(Cs-C24 aryl)-substituted carbamoyl (-(CO)- N(C5-C24 aryl)2), di-N-(Ci-C24 alkyl), N-(C5-C24 aryl)-substituted carbamoyl, thiocarbamoyi (-(CS)-NH ₂ ), mono-(Ci-C24 alkyl)-substituted thiocarbamoyi (-(CS)-NH(Ci-C24 alkyl)), di- (C1-C24 alkyl)-substituted thiocarbamoyi (-(CS)-N(Ci-C24 alkyl)2), mono-(C5-C24 aryl)- substituted thiocarbamoyi (-(CS)-NH-aryl), di-(Cs-C24 aryl)-substituted thiocarbamoyi (- (CS)-N(C5-C24 aryl) ₂ ), di-N-(Ci-C24 alkyl), N-(Cs-C24 aryl)-substituted thiocarbamoyi, carbamido (-NH-(CO)-NH ₂ ), cyano(-C≡N), cyanato (-0-C≡N), thiocyanato (-S-C≡N), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono-(Ci-C24 alkyl)-substituted amino, di-(Ci-C24 alkyl)-substituted amino, mono-(C5-C24 aryl)-substituted amino, di-(Cs- C24 aryl)-substituted amino, (C1 -C24 alkyl)(Cs-C24 aryl)-substituted amino, C2-C24 alkylamido (-NH-(CO)-alkyl), C6-C24 arylamido (-NH-(CO)-aryl), imino (-CR=NH where R = hydrogen, C1-C24 alkyl, Cs-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), C2-C20 alkylimino (-CR=N(alkyl), where R = hydrogen, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), arylimino (-CR=N(aryl), where R = hydrogen, C1 -C20 alkyl, Cs-C24 aryl, C6- C24 alkaryl, C6-C24 aralkyl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonato (- SO2-O ^" ), C1 -C24 alkylsulfanyl (-S-alkyl; also termed "alkylthio"), C5-C24 arylsulfanyl (-S- aryl; also termed "arylthio"), C1-C24 alkylsulfinyl (-(SO)-alkyl), C5-C24 arylsulfinyl (-(SO)- aryl), C1-C24 alkylsulfonyl (-SO2-alkyl), C1 -C24 monoalkylaminosulfonyl -SO2-N(H) alkyl), C1-C24 dialkylaminosulfonyl -SO2-N(alkyl)2, C5-C24 arylsulfonyl (-SO2-aryl), boryl (- BH2), borono (-B(OH)2), boronato (-B(OR)2 where R is alkyl or other hydrocarbyl), phosphono (-P(O)(OH) ₂ ), phosphonato (-P(O)(O ^" )2), phosphinato (-P(O)(O~)), phospho (- PO2), and phosphino (-PH2); and the hydrocarbyl moieties C1-C24 alkyl (preferably C1-C12 alkyl, more preferably C1 -C6 alkyl), C2-C24 alkenyl (preferably C2-C12 alkenyl, more preferably C2-C6 alkenyl), C2-C24 alkynyl (preferably C2-C12 alkynyl, more preferably C2- C6 alkynyl), Cs-C24 aryl (preferably C5-C14 aryl), C6-C24 alkaryl (preferably C6-C16 alkaryl), and C6-C24 aralkyl (preferably C6-C16 aralkyl).

[00037] By "functional ized" as in "functionalized hydrocarbyl," "functionalized alkyl," "functionalized olefin," "functionalized cyclic olefin" and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove. The term "functional group" is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.

[00038] In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above. Analogously, the above-mentioned hydrocarbyl moieties can be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

[00039] "Optional" or "optionally" means that the subsequently described circumstance can or cannot occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase "optionally substituted" means that a non-hydrogen substituent can or cannot be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Olefin Metathesis Catalysts

[00040] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula I):

Formula (I)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L ¹ and L ² are independently neutral electron donor ligands;

n is 0 or 1 ; typically, n is 0; m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom- containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom- containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atoms they are linked to; X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X ¹ and X ² are independently chlorine, bromine, iodine or fluorine;

R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene.

[00041] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (II):

Formula (II)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically M is ruthenium;

L ¹ is a carbene;

L ² is a neutral electron donor ligand;

n is 0 or 1 ; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0; R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to; R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

X ³ and X ⁴ are independently 0 or S; typically, X ³ and X ⁴ are S; and

R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl.

[00042] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula III):

Formula (III)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L ² is a neutral electron donor ligand;

n is 0 or 1 ; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/t-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically X ¹ and X ² are independently chlorine, bromine, iodine or fluorine; and R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR ^3a , N, 0, S, or P; only one of X or Y can be C or CR ^3a ; typically, X and Y are both N;

Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are optionally linked to X or Y via a linker such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or -(CO)-; typically Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are directly linked to X or Y; and

p is 0 when X is O or S, p is 1 when X is N, P or CR ^3a , and p is 2 when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P or CR ^3a , and q is 2 when X is C.

[00043] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula IV):

Formula (IV)

wherein: M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L ² is a neutral electron donor ligand;

n is 0 or 1 ; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR ^3a , N, 0, S, or P; only one of X or Y can be C or CR ^3a ; typically, X and Y are both N;

Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are optionally linked to X or Y via a linker such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or -(CO)-; typically Q ¹ , Q ² , R ³ , R ^3a and R ⁴ are directly linked to X or Y; and

p is 0 when X is O or S, p is 1 when X is N, P or CR ^3a , and p is 2 when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P or CR ^3a , and q is 2 when X is C.

X ³ and X ⁴ are independently O or S; and

R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl.

[00044] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV), wherein R ^x , R ^y , R ^w and R ^z are independently hydrogen, chlorine, fluorine, bromine, iodine, unsubstituted C1-C12 alkyl, unsubstituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, substituted C1-C12 alkyl, substituted C3-C10 cycloalkyl, substituted C5-C24 aryl, unsubstituted heteroalkyl, unsubstituted cycloheteroalkyl, unsubstituted heteroaryl, substituted heteroalkyl, substituted cycloheteroalkyl, substituted heteroaryl. The substitutents can be selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, and carbamate.

[00045] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula V):

Formula (V)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L ² is a neutral electron donor ligand;

n is 0 or 1 ; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X ¹ and X ² are independently chlorine, bromine, iodine or fluorine;

R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR ^3a , or N; only one of X or Y can be C or CR ^3a ; typically, X and Y are both N;

R ^3a is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

Q is a linker, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom- containing hydrocarbylene; generally Q is a two-atom linkage having the structure - [CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t- or -[CR ¹¹ =CR ¹³ ]-; typically Q is -[CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t-, wherein R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted C1 -C12 alkyl, substituted C1 -C12 alkyl, unsubstituted C1 -C12 heteroalkyl, substituted C1 -C12 heteroalkyl, unsubstituted C5-C14 aryl, or substituted C5- Ci4 aryl; "s" and "t" are independently 1 or 2; typically "s" and "t" are independently 1 ; or any two of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure;

R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ³ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ³ is adamantyl, 2-/so-propyl-phenyl, 2,4,6-trimethylphenyl, 2,6-di- /so-propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl; and R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ⁴ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryi), or (C5-C24 aryi) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyi, substituted C1-C20 alkyi, unsubstituted C1-C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryi, substituted C5-C24 aryi, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ⁴ is 2,4,6-trimethylphenyl, 2-/so-propyl-phenyl, 2,6-di-/so- propylphenyl, 2-/so-propyl-6-methylphenyl, or 2-methyl-phenyl.

[00046] In one embodiment of Formula (V), M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L ² is a neutral electron donor ligand;

n is 0 or 1 ; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyi, substituted C1 -C10 alkyi, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryi or substituted C5-C24 aryi; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyi, substituted C1 -C10 alkyi, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryi or substituted C5-C24 aryi; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

X ¹ is a 2-electron anionic donor bridging moiety linking R ³ and Ru;

X ² is a bidentate anionic ligand selected from: nitrate (NO3 ^" ), C1-C20 alkylcarboxylate, C6-C24 arylcarboxylate, C2-C24 acyloxy, C1 -C20 alkylsulfonato, C5-C24 arylsulfonato, C1-C20 alkylsulfanyl, C5-C24 arylsulfanyl, C1 -C20 alkylsulfinyl, or C5-C24 arylsulfinyl; generally X ² is benzoate, pivalate, or nitrate; typically X ² is CF3CO2, CH3CO2, CH3CH2CO2, CFH2CO2, (CH ₃ ) ₃ C02, (CH ₃ ) ₂ CHC02, (CF ₃ )2(CH ₃ )C02, (CF ₃ )(CH ₃ )2C02, benzoate, naphthylate, tosylate, mesylate, or trifluoromethane-sulfonate or nitrate;

R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

X and Y are both N; Q is a linker, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom- containing hydrocarbylene; generally Q is a two-atom linkage having the structure - [CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t- or -[CR ¹¹ =CR ¹³ ]-; typically Q is -[CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t-, wherein R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted C1 -C12 alkyi, substituted C1 -C12 alkyi, unsubstituted C1 -C12 heteroalkyl, substituted C1 -C12 heteroalkyl, unsubstituted C5-C14 aryl, or substituted C5- Ci4 aryl; "s" and "t" are independently 1 or 2; typically "s" and "t" are independently 1 ; or any two of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure;

R ³ is adamantane-2, 1 -diyl; and

R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ⁴ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), or (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyi, substituted C1 -C20 alkyi, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 araikyi, substituted C6-C24 araikyi, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ⁴ is 2,4,6-trimethylphenyl, 2-/so-propyl-phenyl, 2,6-di-/so- propylphenyl, 2-/so-propyl-6-methylphenyl, or 2-methyl-phenyl.

[00047] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (VI):

Formula (VI)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L ² is a neutral electron donor ligand;

n is 0 or 1 ; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1 ; typically, m is 0;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

X ¹ and X ² are independently anionic ligands; generally, X ¹ and X ² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X ¹ and X ² are independently chlorine, bromine, iodine or fluorine;

R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene; X and Y are independently C, CR ^3a , or N; only one of X or Y can be C or CR ^3a ; typically, X and Y are both N;

R ^3a is hydrogen, unsubstituted hydrocarbyi, substituted hydrocarbyi, unsubstituted heteroatom-containing hydrocarbyi, or substituted heteroatom-containing hydrocarbyi;

Q is a linker, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom- containing hydrocarbylene; generally Q is a two-atom linkage having the structure - [CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t- or -[CR ¹¹ =CR ¹³ ]-; typically Q is -[CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t-, wherein R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , are independently hydrogen, unsubstituted hydrocarbyi, substituted hydrocarbyi, unsubstituted heteroatom-containing hydrocarbyi, or substituted heteroatom-containing hydrocarbyi; typically R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, unsubstituted C1 -C12 alkyi, substituted C1 -C12 alkyi, unsubstituted C1 -C12 heteroalkyl, substituted C1 -C12 heteroalkyl, unsubstituted C5-C14 aryl, or substituted C5- Ci4 aryl; "s" and "t" are independently 1 or 2; typically "s" and "t" are independently 1 ; or any two of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure;

R ³ is unsubstituted hydrocarbyi, substituted hydrocarbyi, unsubstituted heteroatom-containing hydrocarbyi, or substituted heteroatom-containing hydrocarbyi; generally, R ³ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyi, substituted C1 -C20 alkyi, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ³ is adamantyl, 2-/so-propyl-phenyl, 2,4,6-trimethylphenyl, 2,6-di- /so-propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl; and

R ⁴ is unsubstituted hydrocarbyi, substituted hydrocarbyi, unsubstituted heteroatom-containing hydrocarbyi, or substituted heteroatom-containing hydrocarbyi; generally, R ⁴ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted (C5-C24 aryl), or (C5-C24 aryl) substituted with up to three substituents selected from unsubstituted C1 -C20 alkyi, substituted C1 -C20 alkyi, unsubstituted C1 -C20 heteroalkyl, substituted C1-C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyi, substituted C6-C24 aralkyi, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ⁴ is 2,4,6-trimethylphenyl, 2-/so-propyl-phenyl, 2,6-di-/so- propylphenyl, 2-/so-propyl-6-methylphenyl, or 2-methyl-phenyl;

X ³ and X ⁴ are independently 0 or S; typically, X ³ and X ⁴ are S; and

R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^x , R ^y , R ^w and R ^z are typically hydrogen, chlorine, florine, bromine, iodine, methyl, ethyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, cyclopropyl, phenyl; typically, R ^x and R ^z are independently chlorine and R ^y and R ^w are independently hydrogen.

[00048] When M is ruthenium, n is 0, m is 0, Q is -[CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t- Ri R^ R ¹³ , and R ¹⁴ , are independently hydrogen, "s" and "t" are independently 1 , and X and Y are both N, the olefin metathesis catalyst represented by the structure of Formula (V) can be represented by the structure of Formula (VII):

Formula (VII)

wherein:

R ¹ is hydrogen; R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

X ¹ and X ² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally, X ¹ and X ² are independently chlorine, bromine, iodine or fluorine; typically, X ¹ and X ² are chlorine;

R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ³ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2- /so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ⁴ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, or C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ⁴ is 2,4,6-trimethylpheny, 2-/so-propyl-phenyl, 2,6-di-/so- propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl.

[00049] In one embodiment of Formula (VII), R ¹ is hydrogen;

R ² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

X ¹ is a 2-electron anionic donor bridging moiety linking R ³ and Ru;

X ² is a bidentate anionic ligand selected from: nitrate (NO3 ^" ), C1-C20 alkylcarboxylate, C6-C24 arylcarboxylate, C2-C24 acyloxy, C1 -C20 alkylsulfonato, C5-C24 arylsulfonato, C1-C20 alkylsulfanyl, C5-C24 arylsulfanyl, C1 -C20 alkylsulfinyl, or C5-C24 arylsulfinyl; generally X ² is benzoate, pivalate, or nitrate; typically X ² is CF3CO2, CH3CO2, CH3CH2CO2, CFH2CO2, (CH ₃ ) ₃ C02, (CH ₃ ) ₂ CHC02, (CF ₃ )2(CH ₃ )C02, (CF ₃ )(CH ₃ )2C02, benzoate, naphthylate, tosylate, mesylate, or trifluoromethane-sulfonate or nitrate;

R ³ is adamantane-2, 1 -diyl; and

R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ⁴ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, or C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1 -C20 alkyl, substituted C1 -C20 alkyl, unsubstituted C1 -C20 heteroalkyl, substituted C1 -C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ⁴ is 2,4,6-trimethylpheny, 2-/so-propyl-phenyl, 2,6-di-/so- propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl.

[00050] In one embodiment of Formula (VII), R ¹ is hydrogen; .e.,

R ¹ and R ² are linked together to form 3-phenylinden-1 -ylidene (i.e., );

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, benzyl or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, benzyl or phenyl; or

R ^a and R ^b are linked to form morpholine or piperidine;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, benzyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, benzyl or phenyl; or

R ^c and R ^d are linked to form morpholine or piperidine; or

R ^b and R ^c are linked to form 1 ,3-dimethylimidazole;

R ³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-isopropyl-6-methyl phenyl; and

R ⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-isopropyl-6-methyl phenyl.

[00051] In one embodiment of Formula (VII), R ¹ is hydrogen;

R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1 -propenyl; or

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, cyclohexyl, benzyl or phenyl;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine; and R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.

[00052] In one embodiment of Formula (VII), R ¹ and R ² are linked to form 3- phenylindeny-1 -ylidene;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/t-butyl, cyclohexyl, benzyl or phenyl;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine; and

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,

2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,

2-/so-propyl-phenyl or 2-methyl-phenyl.

[00053] In one embodiment of Formula (VII), R ¹ and R ² are linked to form 3- phenylindeny-1 -ylidene;

R ^a and R ^b are linked to form morpholine or piperidine;

R ^c and R ^d are linked to form morpholine or piperidine;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine; and

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.

[00054] In one embodiment of Formula (VII), R ¹ and R ² are linked to form 3- phenylindeny-1 -ylidene;

R ^b and R ^c are linked to form 1 ,3-dimethylimidazole; R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine; and

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,

2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl,

2-/so-propyl-phenyl or 2-methyl-phenyl.

[00055] When M is ruthenium, n is 0, m is 0, Q is -[CR ¹¹ R ¹² ] _s -[CR ¹³ R ¹⁴ ]t- R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , are independently hydrogen, "s" and "t" are independently 1 , and X and Y are both N, the olefin metathesis catalyst represented by the structure of Formula (VI) can be represented by the structure of Formula (VIII):

Formula (VIII)

wherein:

R ^a is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^a is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;

R ^b is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^b is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^a and R ^b can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^c is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^c is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R ^d is unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl or substituted C5-C24 aryl; typically R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c and R ^d can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atom they are linked to;

R ^b and R ^c can be linked to form a five-, six- or seven-mem bered heterocycle ring with the nitrogen atoms they are linked to;

R ¹ and R ² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R ² is phenyl, substituted phenyl with at least one substituent selected from: halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, alkylamino, sulfonamide, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, aldehyde, nitrate, cyano, isocyanate, hydroxyl, amine, amide, or carbamate, or substituted alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

R ³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ³ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1-C20 alkyl, substituted C1-C20 alkyl, unsubstituted C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ³ is adamantyl, 2-/so-propyl-phenyl, 2,4,6-trimethylphenyl, 2,6-di- /so-propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl; and

R ⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ⁴ is unsubstituted C3-C10 cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C5-C24 aryl, or C5-C24 aryl substituted with up to three substituents selected from unsubstituted C1-C20 alkyl, substituted C1-C20 alkyl, unsubstituted C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, unsubstituted C5-C24 aryl, substituted C5-C24 aryl, unsubstituted C5-C24 heteroaryl, substituted C5-C24 heteroaryl, unsubstituted C6-C24 aralkyl, substituted C6-C24 aralkyl, unsubstituted C6-C24 alkaryl, substituted C6-C24 alkaryl and halide; typically, R ⁴ is 2,4,6-trimethylphenyl, 2-/so-propyl-phenyl, 2,6-di-/so- propylphenyl, 2-/so-propyl-6-methylphenyl, or 2-methyl-phenyl.

X ³ and X ⁴ are independently 0 or S; typically, X ³ and X ⁴ are S; and

R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R ^x , R ^y , R ^w and R ^z are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R ^x , R ^y , R ^w and R ^z are hydrogen, chlorine, florine, bromine, iodine, methyl, ethyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl, cyclopropyl, phenyl; R ^x and R ^z are independently chlorine and R ^y and R ^w are independently hydrogen.

[00056] In one embodiment of Formula (VIII), R ¹ is hydrogen; R ² is phenyl, 2-iso- propoxy-phenyl, or 2-methyl-1 -propenyl; or R ¹ and R ² are linked together to form 3- phenylinden-1 -ylidene;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl; or

R ^a and R ^b are linked to form morpholine or piperidine;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl; or

R ^c and R ^d are linked to form morpholine or piperidine; or

R ^b and R ^c are linked to form 1 ,3-dimethylimidazole;

X ³ is S;

X ⁴ is S;

R ³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-/so-propyl-6-methyl phenyl;

R ⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2- methyl-phenyl or 2-/so-propyl-6-methyl phenyl;

R ^x , R ^y , R ^w and R ^z are independently hydrogen, chlorine, fluorine, bromine or iodine.

[00057] In one embodiment of Formula (VIII), R ¹ and R ² are linked to form 3- phenylindeny-1 -ylidene;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

X ¹ and X ² are independently chlorine, fluorine, bromine or iodine;

R ^x is chlorine; R ^y is hydrogen; R ^w is hydrogen; R ^z is chlorine; R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.

[00058] In one embodiment of Formula (VIII), R ¹ and R ² are linked to form 3- phenylindeny-1 -ylidene;

R ^b and R ^c are linked to form 1 ,3-dimethylimidazole;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/t-butyl, cyclohexyl, benzyl or phenyl;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine;

R ^x is chlorine; R ^y is hydrogen; R ^w is hydrogen; R ^z is chlorine;

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.

[00059] In one embodiment of Formula (VIII), R ¹ and R ² are linked to form 3- phenylindeny-1 -ylidene;

R ^a and R ^b are linked to form morpholine or piperidine;

R ^c and R ^d are linked to form morpholine or piperidine;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine;

R ^x is chlorine; R ^y is hydrogen; R ^w is hydrogen; R ^z is chlorine;

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.

[00060] In one embodiment of Formula (VIII), R ¹ is hydrogen;

R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1 -propenyl;

R ^b and R ^c are linked to form 1 ,3-dimethylimidazole; R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine;

R ^x is chlorine; R ^y is hydrogen; R ^w is hydrogen; R ^z is chlorine;

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.

[00061] In one embodiment of Formula (VIII), R ¹ is hydrogen;

R ² is phenyl, 2-iso-propoxy-phenyl or 2-methyl-1 -propenyl;

R ^a and R ^b are linked to form morpholine or piperidine;

R ^c and R ^d are linked to form morpholine or piperidine;

X ¹ and X ² are independently chlorine, bromine, fluorine or iodine;

R ^x is chlorine; R ^y is hydrogen; R ^w is hydrogen; R ^z is chlorine;

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl, 2-/so-propyl-phenyl or 2-methyl-phenyl.

[00062] Examples of olefin metathesis catalysts represented by the structure of Formula (VII) are described in Table (1 ).

Table (1 ): Examples of olefin metathesis catalysts represented by the structure of

Formula (VII), wherein X ¹ is CI and X ² is CI

42







53

[00063] Examples of olefin metathesis catalysts represented by the structure of Formula (VIII) are described in Table (2).

Table (2): Examples of olefin metathesis catalysts represented by the structure of Formula (VIII), wherein: R ^y is H, R ^w is H, R ^x is CI, R ^z is CI, X ³ is S and X ⁴ is S.

60

239 adamantyl Mes Bz Bz

240 Mipp Mipp Bz Bz

241 DIPP DIPP Bz Bz

242 IPP IPP Bz Bz

[00064] When M is ruthenium, n is 0, m is 0, Q is -[CR ¹¹ =R ¹³ ]-, R ¹¹ and R ¹³ are independently hydrogen, and X and Y are both N, the olefin metathesis catalyst represented by the structure of Formula (V) can be represented by the structure of Formula (IX):

Formula (IX)

wherein:

R ¹ is hydrogen, R ² is unsubstituted phenyl, substituted phenyl or alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl; or R ^a and R ^b are linked to form morpholine or piperidine;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; or R ^c and R ^d are linked to form morpholine or piperidine; or R ^b and R ^c are linked to form 1 ,3-dimethylimidazole;

X ¹ and X ² are independently chlorine, bromine, iodine or fluorine; X ¹ and X ² are chlorine;

R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl- phenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2-/so- propyl-6-methylphenyl or 2-methyl-phenyl.

[00065] In one embodiment of Formula (IX),

R ¹ is hydrogen,

R ² is unsubstituted phenyl, substituted phenyl or alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl; or R ^a and R ^b are linked to form morpholine or piperidine;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; or R ^c and R ^d are linked to form morpholine or piperidine; or R ^b and R ^c are linked to form 1 ,3-dimethylimidazole;

X ¹ is a 2-electron anionic donor bridging moiety linking R ³ and Ru;

X ² is CF3CO2, CH3CO2, CH3CH2CO2, CFH2CO2, (CH ₃ ) ₃ C02, (CH ₃ ) ₂ CHC02, (CF ₃ )2(CH ₃ )C02, (CF ₃ )(CH ₃ ) ₂ C02, benzoate, naphthylate, tosylate, mesylate, or trifluoromethane-sulfonate or nitrate;

R ³ is adamantane-2, 1 -diyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2-iso- propyl-6-methylphenyl or 2-methyl-phenyl.

[00066] In one embodiment of Formula (IX), R ¹ is hydrogen;

R ² is phenyl, 2-/so-propoxy-phenyl or 2-methyl-1 -propenyl; or

R ¹ and R ² are linked together to form 3-phenylinden-1 -ylidene;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, or phenyl; or R ^a and R ^b are linked to form morpholine or piperidine;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ie/f-butyl, or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, or phenyl; or R ^c and R ^d are linked to form morpholine or piperidine; or R ^b and R ^c are linked to form 1 ,3- dimethylimidazole;

X ¹ and X ² are chlorine;

R ³ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl; and

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl.

[00067] When M is ruthenium, n is 0, m is 0, Q is -[CR ¹¹ =R ¹³ ]-, R ¹¹ and R ¹³ are independently hydrogen, and X and Y are both N, the olefin metathesis catalyst represented by the structure of Formula (VI) can be represented by the structure of Formula (X):

R ^c

R ^b'

Formula (X)

wherein:

R ¹ is hydrogen,

R ² is unsubstituted phenyl, substituted phenyl or alkenyl; or R ¹ and R ² are linked together to form an optionally substituted indenylidene;

R ^a is methyl, ethyl, n-propyl, /so-propyl, n-butyl, ierf-butyl, cyclohexyl, benzyl or phenyl;

R ^b is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl; or R ^a and R ^b are linked to form morpholine or piperidine;

R ^c is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl or phenyl;

R ^d is methyl, ethyl, n-propyl, /so-propyl, n-butyl, fe/f-butyl, cyclohexyl, benzyl or phenyl; or R ^c and R ^d are linked to form morpholine or piperidine; or R ^b and R ^c are linked to form 1 ,3-dimethylimidazole;

R ³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl- phenyl, 2-/so-propyl-6-methylphenyl or 2-methyl-phenyl;

R ⁴ is 2,4,6-trimethylphenyl, 2,6-di-/so-propylphenyl, 2-/so-propyl-phenyl, 2-/so- propyl-6-methylphenyl or 2-methyl-phenyl.

X ³ and X ⁴ are S;

R ^x and R ^z are independently chlorine; and

R ^y and R ^w are independently hydrogen.

[00068] The catalysts of the invention may be attached to a solid support. [00069] The present invention also concerns processes for synthesizing the olefin metathesis catalysts of the invention. The olefin metathesis catalysts according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry. For example, synthetic Scheme 1 , set forth below, illustrates how the compounds according to the invention can be synthesized.

Scheme 1

Formula (V)

wherein: M, R ¹ , R ² , R ³ , R ⁴ , R ^a , R ^b , R ^c , R ^d , X ¹ , X ² , Q, n, m, L ² , X, and Y are as defined herein, and R ^s , R ^l , and R ^u are each independently substituted C5-C24 aryl, unsubstituted C5-C24 aryl or substituted C1-C10 alkyl, unsubstituted C1-C10 alkyl; generally R ^s , R ^l , and R ^u are each independently unsubstituted C5-C24 aryl; typically R ^s , R ^l , and R ^u are each independently phenyl or cycohexyl.

[00070] In a typical procedure an olefin metathesis catalyst of general Formula (A) is reacted at room temperature with tosyl chloride (TsCI) and an excess of thiourea derivative to produce an olefin metathesis catalyst of general Formula (V).

[00071] In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (VI) starting with an olefin metathesis catalyst of Formula (V): Scheme 2

Formula (V) Formula (VI) wherein: M, R ¹ , R ² , R ³ , R ⁴ , R ^a , R ^b , R ^c , R ^d , X ¹ , X ² , Q, n, m, L ² , X, Y, R ^x , Rv, R ^w , R ^z , X ³ and X ⁴ are as defined herein.

[00072] In a typical procedure as shown in Scheme 2, the thiourea olefin metathesis catalyst represented by the structure of Formula (V) can become a dithiolate derivative olefin metathesis catalyst represented by the structure of Formula (VI).

[00073] In another embodiment, the invention concerns methods of using the olefin metathesis catalysts of the invention, in the synthesis of related olefin metathesis catalysts. The ruthenium olefin metathesis catalysts bearing labile thiourea ligands of the invention, are excellent precursors for various Second Generation Grubbs ruthenium olefin metathesis catalysts. The Second Generation Grubbs ruthenium olefin metathesis catalysts synthesized during these procedures are obtained in very high yield and with very high purity, which presents an advantage compared to the existing synthetic procedures.

[00074] In one embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (B) starting with an olefin metathesis catalyst of Formula (V): Scheme 3

Formula (V)

wherein:

R ¹ , R ² , R ³ , R ⁴ , R ^a , R ^b , R ^c , R ^d , X ¹ , X ² , Q, n, m, L ² , X and Y are as defined herein and "L" is selected from PR ^g OR ^h OR', PR ^k R ^e OR ^f , pyridine, trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n-butylphosphine (PBu3), tri(ortho-tolyl)phosphine (P-o- toly ), tri-tert-butylphosphine (P-fe/f-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), tri-/so-propylphosphine (P-i-Pr3), trioctylphosphine (POct3), tri-/so-butylphosphine, (P-1-BU3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(C6F5)3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), diethylphenylphosphine (PEt2Ph), phosphabicycloalkane, substituted pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, or triazine;

R ^g is unsubstituted C1 -C10 alkyl, substituted C1-C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyi or unsubstituted C3-C8 cycloalkyi; generally, R ^g is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically R ^g is phenyl;

R ^h is unsubstituted C1 -C10 alkyl, substituted C1-C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyi or unsubstituted C3-C8 cycloalkyi; generally R ^h is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R ^h is phenyl or methyl;

R' is unsubstituted C1 -C10 alkyl, substituted C1 -C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R' is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R' is phenyl or methyl;

R ^k is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R ^k is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R ^k is phenyl;

R ^e is unsubstituted C1 -C10 alkyl, substituted C1-C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R ^e is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically R ^e is phenyl;

R ^f is unsubstituted C1-C10 alkyl, substituted C1 -C10 alkyl, substituted C6-C10 aryl, unsubstituted C6-C10 aryl, substituted C3-C8 cycloalkyl or unsubstituted C3-C8 cycloalkyl; generally, R ^f is methyl, ethyl, /so-propyl, n-butyl, sec-butyl, fe/f-butyl, 4-methoxyphenyl, benzyl or phenyl; typically, R ^f is phenyl, methyl, /so-propyl or 4-methoxyphenyl.

[00075] The ligand exchange reactions are carried out under inert atmosphere (under nitrogen or argon). The reactions generally are carried out at room temperature or at temperatures from 15°C to 25°C or from 25°C to 60°C, or from 35°C to 50°C or from 20°C to 25°C, or from 30°C to 40°C, or from 25°C to 45°C. The reaction times vary from several minutes to several hours 12 hours, 24 hours or 48 hours. Generally, the reactions take place in solvents such as tetrahydrofuran (THF), benzene, toluene, xylene, diethyl ether, dioxane, alcohols, methyl-tetrahydrofuran, acetone, ethyl acetate, methyl fe/f-butyl ether (MTBE), dimethylformamide (DMF), and dichloromethane.

[00076] In one embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (C) starting with an olefin metathesis catalyst of Formula (VII), as shown in Scheme 4, wherein: R ¹ , R ² , R ³ , R ⁴ , R ^a , R ^b , R ^c , R ^d , X ¹ , X ² , R ^k , R ^e and R ^f are as defined herein. Scheme 4

Formula (VII)

[00077] In one embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (D) starting with an olefin metathesis catalyst of Formula (VII), as shown in Scheme 5, wherein: R ¹ , R ² , R ³ , R ⁴ , R ^a , R ^b , R ^c , R ^d , X ¹ , X ² , R9, R ^h and R' are as defined herein.

Scheme 5

Formula (D)

Formula (VII) [00078] At this stage, those skilled in the art will appreciate that many additional compounds that fall under the scope of the invention can be prepared by performing various common chemical reactions. Details of certain specific chemical transformations are provided in the examples.

[00079] The metal carbene olefin metathesis catalysts can be utilized in olefin metathesis reactions according to techniques known in the art. For example, the metal carbene olefin metathesis catalysts are typically added to a resin composition as a solid, a solution, or as a suspension. When the metal carbene olefin metathesis catalysts are added to a resin composition as a suspension, the metal carbene olefin metathesis catalysts are suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-/so-propylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst(s), and which is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boiling impurity in the olefin metathesis reaction. It will be appreciated that the amount of catalyst that is used (i.e., the "catalyst loading") in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading can be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of an olefinic substrate (e.g., cyclic olefins).

Cyclic Olefins

[00080] Resin compositions that may be used with the present invention disclosed herein comprise one or more cyclic olefins. Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or polyunsaturated C5 to C24 hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition.

[00081] Examples of bicyclic and polycyclic olefins thus include, without limitation, dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tncyclopentadiene (cyclopentadiene thmer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; C2-C12 hydrocarbyl substituted norbornenes; 5-butyl-2-norbornene; 5-hexyl- 2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5- vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-/sopropenyl-2-norbornene; 5-propenyl- 2-norbornene; 5-butenyl-2-norbornene; 5-tolyl-norbornene; 5-methyl-2-norbornene; 5- ethyl-2-norbornene; 5-/sobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5- phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5- methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1 -norbornene; 5-methyl-5-methoxy- carbonylnorbornene; bicyclo[2.2.1 ]hept-2-ene-2-carboxylic acid, 2-ethylhexyl ester; 5- cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo- 5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6- dimethoxy carbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyl tetracyclododecene; 8-ethyltetracyclododecene; 8-methoxy carbonyltetracyclo dodecene; 8-methyl-8-tetra cyclododecene; 8-cyanotetracyclo dodecene; pentacyclopentadecene; pentacyclo hexadecene; bicyclo[2.2.1 ]hept-2-ene-5- phenoxymethyl; 2-ethylhexyl ester-bicyclo[2.2.1 ]hept-5-ene-2-carboxylic acid; 2- hydroxyethyl ester-bicyclo[2.2.1 ]hept-5-ene-2-carboxylic acid; bicyclo[2.2.1 ]hept-5-ene- 2-methanol; bicyclo[2.2.1 ]hept-5-ene-2-heptanoic acid-methyl ester; bicyclo[2.2.1 ]hept-5- ene-2-hexanoic acid-methyl ester; 1 ,4:5,8-dimethanonaphthalene, 2-hexyl-1 ,2, 3, 4, 4a, 5, 8,8a-octahydro; bicyclo[2.2.1 ]hept-5-ene-2-octanoic acid-methyl ester; 1 ,4:5,8- dimethano naphthalene; 2-butyl-1 ,2,3,4,4a,5,8,8a-octahydro; ethyl idenetetracyclododecene; 2-vinyl-1 ,2,3,4,4a,5,8,8a-octahydro-1 ,4:5,8-dimethano naphthalene; and the like, and their structural isomers, stereoisomers, and mixtures thereof.

EXPERIMENTAL

General Information - Materials and Methods

[00082] In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. The examples are to be considered as not being limiting of the invention described herein.

[00083] All reactions involving metal complexes were conducted in oven-dried glassware under an argon or nitrogen atmosphere using standard Schlenk techniques. Chemicals and solvents were obtained from Sigma-Aldrich, Strem, Alfa Aesar, Nexeo, Brenntag, AG Layne and TCI. Commercially available reagents were used as received unless otherwise noted. Silica gel was purchased from Fisher (0.040-0.063 pm, EMD Millipore).

[00084] The crystallographic measurements were performed at 100(2) K using a Bruker APEX-II CCD area detector diffractometer (Μο- α radiation, λ = 0.71073 A). In each case, a specimen of suitable size and quality was selected and mounted onto a nylon loop. The structures were solved by direct methods, which successfully located most of the nonhydrogen atoms. Semi-empirical absorption corrections were applied. Subsequent refinement on F ² using the SHELXTL/PC package (version 6.1 ) allowed location of the remaining non-hydrogen atoms.

[00085] Ultrene® 99 dicyclopentadiene (DCPD) was obtained from Cymetech Corporation. A modified DCPD base resin containing 20-25% tricyclopentadiene (and small amounts of higher cyclopentadiene homologs) (DCPD-HT) was prepared by heat treatment of Ultrene® 99 DCPD generally as described in U.S. Pat. No. 4,899,005.

[00086] Catalysts C931 , C933, C793, C827, C929, C785ss, C765ss, and C848 were prepared using known methods.

[00087] ¹ H and ¹³ C NMR spectra were recorded on a Varian 400 MHz spectrometer. Chemical shifts are reported in ppm downfield from Me ₄ Si by using the residual solvent peak as an internal standard (CDC - δ 7.24 ppm; CD2CI2 - δ 5.32 ppm). Spectra were analyzed and processed using MestReNova software.

[00088] GC Method used in Example 9: Column: HP-5, 30m x 0.25mm (ID) x 0.25pm film thickness; Manufacturer: Agilent; GC and column conditions: Injector temperature: 250 °C, Detector temperature: 280 °C; Oven temperature: Starting temperature: 100 °C, hold time: 1 minute; Ramp rate 10 °C/min to 270 °C, hold time: 12 minutes; Carrier gas: Helium; Average velocity: 30 cm/sec; Split ratio: 40.8: 1 .

[00089] The following abbreviations are used in the examples: ml_ milliliter

DCM dichlorom ethane

CD2CI2 deuterated dichlorom ethane

CDC deuterated chloroform

GC gas chromatography

C931

[1 .3-b!S-(2,4,6-trimethylphenyi)-2- imidazo!idinyiidene]dichloro

(phenylindenyIidene)(triphenyiphosphine)ruthenium(l [CAS 340810-50-6]

C793

[1 ,3-Bis(2-methylphenyl)-2- imidazolidinylidene]dichloro(benzylidene)

(tricyclohexylphosphine)ruthenium(ll)

[CAS 927429-60-5]

Dichloro[1 ,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene](3-methyl-2- butenylidene)(tricyclohexylphosphine)rutheni -91 -4]

Dichloro[1 ,3-bis(2,6-diisopropylphenyl)-2- imidazolidinylidene](benzylidene)(tricyclohexylphosphi ne)ruthenium(ll)

[CAS 373640-75-6]

Dichloro[1 ,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene](benzylidene)(tricyclohexylphosphi ne)ruthenium(ll)

[CAS 246047-72-3]

DMSO dimethylsulfoxide

PCys tricyclohexylphosphine

C929

Dichloro[1 ,3-dihydro-1 ,3-bis(2,4,6-trimethylphenyl)- 2/-/imidazol-2-ylidene](3-phenyl-1 /-/-inden-1 -ylidene) (triphenylphosphine)-, (SP-5-41 )- ruthenium(ll)

[CAS 254972-47-9]

EtOAc ethyl acetate

MTBE methyl fe/f-butyl ether

EXAMPLES

[00090] Example 1

Synthesis of C801TU

C801 _TU

[00091] To a 40 mL scintillation vial equipped with a magnetic stir bar was added C931 (1 .00 g, 1 .07 mmol), p-toluenesulfonyl chloride (0.102 g, 0.537 mmol), tetramethylthiourea (0.426 g, 3.22 mmol), and 3 mL dichloromethane. The reaction was stirred at ambient temperature for thirty minutes then slowly diluted with diethyl ether (35 mL). The resulting solution was stirred for an additional hour affording a red microcrystalline solid that was isolated by filtration, washed with diethyl ether (2 x 10 mL) then dried in vacuum to afford C801 TU (0.706 g, 82.1 % yield). The X-ray structure of C801 TU is shown in Figure 1 .

[00092] ¹ H NMR (400 MHz, CDC ) δ 8.79 (d, J = 6.8 Hz, 1 H), 7.74 (d, J = 7.2 Hz, 2H), 7.46 (t, J = 7.3 Hz, 1 H), 7.36 (t, J = 7.6 Hz, 2H), 7.25 - 7.18 (m, 2H), 7.16 (s, 1 H), 7.1 1 (d, J = 7.9 Hz, 1 H), 7.05 (s, 1 H), 7.03 (s, 1 H), 6.41 (s, 1 H), 6.20 (s, 1 H), 4.19 - 4.04 (m, 2H), 4.04 - 3.93 (m, 1 H), 3.90 - 3.76 (m, 1 H), 2.77 (s, 3H), 2.62 (s, 3H), 2.58 (s, 12H), 2.43 (s, 3H), 2.31 (s, 3H), 1 .89 (s, 3H), 1 .75 (s, 3H).

[00093] Example 2

Synthesis of C701TU

C701 _TU

[00094] To a 40 mL scintillation vial equipped with a magnetic stir bar was added C848 (1 .00 g, 1 .18 mmol), p-toluenesulfonyl chloride (0.1 12 g, 0.589 mmol), tetramethylthiourea (0.623 g, 4.71 mmol), and 10 mL dichloromethane. The reaction was stirred at ambient temperature for thirty minutes then passed through a syringe filter and transferred to a 250 mL round bottom flask equipped with a magnetic stir bar. The reaction mixture was slowly combined with diethyl ether (30 mL) followed by hexanes (40 mL) and allowed to stir for an additional hour. The resulting green microcrystalline precipitate was isolated by filtration, washed with hexanes (2 x 10 mL) then dried in vacuum to afford C701 TU (0.422 g, 51 .2% yield).

[00095] ¹ H NMR (400 MHz, CD2CI2) δ 18.09 (s, 1 H), 7.74 (d, J = 7.5 Hz, 2H), 7.44 (t, J = 7.3 Hz, 1 H), 7.13 (t, J = 7.8 Hz, 2H), 7.00 (s, 2H), 6.68 (s, 2H), 4.10 - 4.01 (m, 2H), 3.96 - 3.87 (m, 2H), 2.59 (s, 6H), 2.57 (s, 12H), 2.32 (s, 3H), 2.25 (s, 3H), 2.18 (s, 6H).

[00096] Example 3

Synthesis of C885TU

C885JU [00097] To a 20 mL scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.268 mmol), dimorpholino methanethione (0.290 g, 1 .34 mmol), and diethyl ether (10 mL). The reaction was stirred at ambient temperature for 18 hours. The resulting precipitate was isolated by filtration, washed with diethyl ether (3 x 10 mL), hexanes (1 x 10 mL) then dried in vacuum to afford C885TU (0.467 g, 98.3% yield).

[00098] ¹ H NMR (400 MHz, CDCb) δ 8.72 (d, J = 7.4 Hz, 1 H), 7.69 (d, J = 7.2 Hz, 2H), 7.47 (t, J = 7.4 Hz, 1 H), 7.36 (t, J = 7.6 Hz, 2H), 7.26 - 7.17 (m, 2H), 7.08 (d, J = 7.0 Hz, 1 H), 7.06 (s, 1 H), 7.02 (s, 1 H), 6.93 (s, 1 H), 6.37 (s, 1 H), 6.29 (s, 1 H), 4.16 - 3.91 (m, 3H), 3.86 - 3.78 (m, 1 H), 3.35 (br s, 8H), 3.22 - 3.09 (m, 4H), 3.07 - 2.97 (m, 4H), 2.79 (s, 3H), 2.60 (s, 3H), 2.44 (s, 3H), 2.36 (s, 3H), 1 .85 (s, 3H), 1.77 (s, 3H).

[00099] Example 4

Synthesis of C881TU

[000100] To a 20 mL scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.268 mmol), di(piperidin-1 -yl)methanethione (0.285 g, 1 .34 mmol), and diethyl ether (10 mL). The reaction was stirred at ambient temperature for 18 hours. The resulting precipitate was isolated by filtration, washed with diethyl ether (3 x 10 mL), hexanes (1 x 10 mL) then dried in vacuum to afford C881 TU (0.435 g, 92.0% yield).

[000101] ¹ H NMR (400 MHz, CDCb) δ 8.80 (d, J = 6.7 Hz, 1 H), 7.69 (d, J = 7.2 Hz, 2H), 7.45 (t, J = 7.2 Hz, 1 H), 7.36 (t, J = 7.5 Hz, 2H), 7.19 (dt, J = 14.0, 6.9 Hz, 2H), 7.09 - 6.96 (m, 4H), 6.41 (s, 1 H), 6.27 (s, 1 H), 4.21 - 3.92 (m, 3H), 3.89 - 3.75 (m, 1 H), 2.95 (s, 8H), 2.77 (s, 3H), 2.58 (s, 3H), 2.45 (s, 3H), 2.34 (s, 3H), 1 .88 (s, 3H), 1 .76 (s, 3H), 1 .28 (s, 12H). [000102] Example 5

Synthesis of C799TU

C799 _TU

[000103] To a 20 ml_ scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.268 mmol), 1 ,3- dimethylimidazolidine-2-thione (0.177 g, 1 .34 mmol), and diethyl ether (10 ml_). The reaction was stirred at ambient temperature for 18 hours. The resulting precipitate was isolated by filtration, washed with diethyl ether (3 x 10 ml_), hexanes (1 x 10 ml_) then dried in vacuum to afford C799TU (0.409 g, 95.3% yield).

[000104] ¹ H NMR (400 MHz, CDC ) δ 8.77 (d, J = 6.1 Hz, 1 H), 7.72 (d, J = 7.4 Hz, 2H), 7.46 (t, J = 7.3 Hz, 1 H), 7.35 (t, J = 7.6 Hz, 2H), 7.25 - 7.18 (m, 2H), 7.12 - 7.05 (m, 3H), 7.02 (s, 1 H), 6.42 (s, 1 H), 6.21 (s, 1 H), 4.20 - 3.93 (m, 3H), 3.89 - 3.77 (m, 1 H), 3.39 (s, 4H), 2.78 (s, 3H), 2.61 (s, 3H), 2.43 (s, 3H), 2.32 (s, 9H), 1 .86 (s, 3H), 1 .75 (s, 3H).

[000105] Example 6

Synthesis of C951 TU

C951 _TU

[000106] To a 20 ml_ scintillation vial equipped with a magnetic stir bar were added C931 (0.400 g, 0.430 mmol), p-toluenesulfonyl chloride (0.041 g, 0.21 mmol), 1 ,3- dibenzyl imidazolidine-2-thione (0.303 g, 1 .07 mmol), and 10 ml_ diethyl ether. The reaction was stirred at ambient temperature overnight and the resulting precipitate was isolated by filtration. The solid was subsequently recrystallized by slow diffusion of hexanes into a concentrated dichloromethane solution at -35 °C. The resulting red crystalline solid was isolated by filtration, washed with hexanes (2 x 10 mL) then dried in vacuum to afford C951 TU (0.157 g, 38.4% yield).

[000107] ¹ H NMR (400 MHz, CD2CI2) δ 8.81 -8.77 (m, 1 H), 7.70 (d, J = 7.2 Hz, 2H), 7.50 (t, J = 7.5 Hz, 1 H), 7.40 (d, J = 7.7 Hz, 2H), 7.36 (d, J = 7.1 Hz, 2H), 7.23 - 7.14 (m, 6H), 7.10 (s, 1 H), 7.06-7.01 (m, 1 H), 7.00-6.91 (m, 5H), 6.90 (s, 1 H), 6.46 (s, 1 H), 6.24 (s, 1 H), 4.22 - 3.96 (m, 5H), 3.92 - 3.81 (m, 3H), 3.22 (s, 4H), 2.81 (s, 3H), 2.59 (s, 3H), 2.47 (s, 3H), 1 .96 (s, 3H), 1 .87 (s, 3H), 1 .75 (s, 3H).

[000108] Example 7

Synthesis of C799UTU

[000109] To a 20 mL scintillation vial equipped with a magnetic stir bar was added C929 (0.400 g, 0.431 mmol), p-toluenesulfonyl chloride (0.041 g, 0.215 mmol), tetramethylthiourea (0.142 g, 1.07 mmol), and diethyl ether (8 mL). The reaction was stirred at ambient temperature for 18 hours. The resulting precipitate was isolated by filtration, washed with methanol (2 x 5 mL), diethyl ether (2 x 10 mL), hexanes (1 x 10 mL) then dried in vacuum to afford C799UTU (0.146 g, 42.4% yield).

[000110] ¹ H NMR (400 MHz, CD2CI2) δ 8.70 (d, J = 7.3 Hz, 1 H), 7.77 (d, J = 7.3 Hz, 2H), 7.51 (t, J = 7.4 Hz, 1 H), 7.41 (t, J = 7.6 Hz, 2H), 7.30 (t, J = 7.3 Hz, 1 H), 7.24 - 7.14 (m, 4H), 7.12 (s, 1 H), 7.08 (s, 1 H), 7.00 (s, J = 1 .7 Hz, 1 H), 6.45 (s, 1 H), 6.24 (s, 1 H), 2.61 (s, 12H), 2.52 (s, 3H), 2.39 (s, 3H), 2.37 (s, 3H), 2.16 (s, 3H), 1 .80 (s, 3H), 1 .70 (s, 3H). [000111] Example 8

Synthesis of C839ss

[000112] To a 40 mL scintillation vial equipped with a magnetic stir bar was added C701 -RJ (0.250 g, 0.357 mmol), (3,6-dichlorobenzene-1 ,2-dithiolato) (ethylene diamine)zinc(ll) (259 mg, 0.774 mmol), and 4 mL tetrahydrofuran. The resulting suspension was stirred for one hour at room temperature then devolatilized. The resulting residue was redissolved in a minimal amount of dichloromethane, passed through a syringe filter, then slowly combined with hexanes (30 mL). The brown microcrystalline product was isolated by filtration, washed with hexanes (2 x 5 mL) and dried in vacuum to afford C839ss (0.179 g, 59.6%).

[000113] ¹ H NMR (400 MHz, CD2CI2) δ 16.08 (s, 1 H), 7.18 (t, J = 7.3 Hz, 1 H), 7.00 (d, J = 7.8 Hz, 1 H), 6.93 (d, J = 8.2 Hz, 1 H), 6.87 (s, 2H), 6.79 (t, J = 7.7 Hz, 2H), 6.71 - 6.52 (br s, 2H), 6.44 (d, J = 7.2 Hz, 2H), 4.03 - 3.80 (m, 4H), 2.72 (s, 12H), 2.50 (br s, 12H), 2.18 (s, 6H).

Catalytic Activity of Complexes

[000114] Example 9

Ring Closing Metathesis Reaction of Diethyl Diallylmalonate

[000115] An NMR tube with a screwcap septum top was charged inside an argon filled glovebox with catalyst stock solution (0.050 mL, 0.016 M, 0.0008 mmol, 1 mol %) and CD2CI2 (0.750 mL). Samples were equilibrated at 30 °C in the NMR probe before diethyl diallylmalonate (0.0193 mL, 0.0798 mmol) was added via syringe. Data points were collected over 30 minutes using the Varian array function. The conversion to diethyl cyclopent-3-ene-1 , 1 -dicarboxylate was determined by comparing the ratio of the integrals of the methylene protons in the starting material and product (δ 2.62 (dt) and 3.00 (s) respectively).

[000116] The ruthenium catalysts were benchmarked against the ring closing metathesis of diethyl diallylmalonate and compared to the standard C627. Reactions catalyzed by thiourea bearing complexes were extremely rapid and afforded complete conversion to diethyl cyclopent-3-ene-1 , 1 -dicarboxylate in less than 10 minutes whereas C627 required approximately 25 minutes (Figure 2). The relative reactivity of the novel complexes assayed was C799TU > C885TU > C801 TU > C881 TU > C799UTU.

[000117] Example 10

Self-Metathesis of Trans-Methyl Oleate

[000118] In an argon filled glovebox, a 4 ml_ scintillation vial equipped with a magnetic stir bar was charged with 0.0044 mmol, 1 mol % ruthenium catalyst and tetrahydrofuran (1 ml_). Trans-methyl-9-octadecenoate (MO) (0.150 ml_, 0.442 mmol) was subsequently added, the vial was sealed and stirred at ambient temperature. Samples were analyzed by gas chromatography to determine yields and stereoselectivies and the results are shared in Table (3).

[000119] At 1 mol % catalyst loading C765ss, a previously identified stereoretentive catalyst, afforded minimal conversion (<1 %). Both C785ss and C839ss afforded highly stereoretentive transformations (> 98% E or trans). While C785ss afforded 34 % conversion after 8 hours, complete conversion (~50%) was achieved by C839ss in 3 hours. Erosion of stereoselectivity was observed at longer reaction times. Table (3) entry time (h) [Ru] % MO (% £) % 9C18 (% £J % DE (% £)

1 1 C765ss 100 (>99) 0 (>99) 0 (>99)

3 99 (>99) 0.2 (>99) 0.2 (>99)

5 99 (>99) 0.2 (>99) 0.2 (>99)

8 99 (>99) 0.3 (>99) 0.3 (>99)

2 1 C785ss 92 (>99) 4 (>99) 4 (>99)

3 80 (>99) 10 (99) 10 (99)

5 73 (99) 14 (99) 13 (99)

8 66 (99) 17 (98) 17 (98)

3 1 C839 _ss 64 (>99) 18 (>99) 18 (>99)

3 52 (98) 24 (98) 24 (98)

5 51 (94) 25 (94) 24 (95)

8 50 (91 ) 25 (91 ) 25 (91 )