GAO PENGCHENG (US)
US20080233410A1 | 2008-09-25 | |||
US20110028513A1 | 2011-02-03 |
CLAIMS What is claimed is: 1. A compound of formula (I) selected from the group consisting of: wherein: T1 is N or CRa1; T2 is N or CRa2; T3 is N or CRa3; X is a counter anion; Y1, if present, is selected from the group consisting of ORb1 and N(Rb1)(Rb2); Y2, if present, is selected from the group consisting of N(Rb1)(Rb2) and optionally substituted phenyl; Z is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C8 heteroaryl, wherein each optional substituent in Z is independently at least one selected from the group consisting of H, halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, ORA, N(RA)(RB), C(=O)RA, C(=O)N(RA)(RB), C(=O)ORB, N(RA)S(=O)2RB, S(=O)2N(RA), optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C12 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein the C1-C6 alkyl, C3-C8 cycloalkyl, C2-C12 heterocyclyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl are each optionally substituted with at least one substituent selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl; Ra1, Ra2, Ra3, Ra5, and Ra6, if present, are each independently selected from the group consisting of H, halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, ORA, N(RA)(RB), C(=O)RA, C(=O)N(RA)(RB), C(=O)ORB, N(RA)S(=O)2RB, S(=O)2N(RA), optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of Ra1, Ra2, Ra3, Ra5, and Ra6 is independently selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of Ra1, Ra2, Ra3, Ra5, and Ra6 may combine with the carbon atoms to which they are bound to form an optionally substituted C5-C12 cycloalkyl, optionally substituted C2-C12 heterocyclyl, or optionally substituted C6-C10 aryl; Ra4 is selected from the group consisting of H, C1-C6 alkyl, C6-C10 aryl, and C2-C12 heterocyclyl; Rb1 and Rb2 are each independently selected from the group consisting of H, optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein Rb1 and Rb2 may combine with the atom to which they are bound to form an optionally substituted C2-C12 heterocyclyl, wherein each optional substituent in each of Rb1 and Rb2 is independently selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl; and RA and RB are each independently selected from the group consisting of H, C1-C6 alkyl, C1-C3 haloalkyl, C2-C6 alkenyl, benzyl, naphthyl, C4-C10 heteroaryl, and phenyl, wherein each substituent in RA and RB is optionally substituted with at least one substituent selected from the group consisting of CN, NO2, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, and halogen. 2. The compound of claim 1, wherein at least one of the following occurs: ( T1 is CRa1; ( T2 is CRa2; and ( T3 is CRa3. 3. The compound of claim 1 or 2, wherein Z is: , wherein: Rc1, Rc2, Rc3, Rc4, and Rc5 are each independently selected from the group consisting of H, halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, ORA, N(RA)(RB), C(=O)RA, C(=O)N(RA)(RB), C(=O)ORB, N(RA)S(=O)2RB, S(=O)2N(RA), optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C12 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of Rc1, Rc2, Rc3, Rc4, and Rc5 is independently selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of Rc1, Rc2, Rc3, Rc4, and Rc5 may combine with the carbon atoms to which they are bound to form an optionally substituted C5-C12 cycloalkyl, optionally substituted C2-C12 heterocyclyl, or optionally substituted C6-C10 aryl. 4. The compound of any one of claims 1-3, wherein at least one of the following occurs: (a) at least one of Ra1, Ra2, and Ra3 is H; (b) at least two of Ra1, Ra2, and Ra3 are H; and (c) each of Ra1, Ra2, and Ra3 are H. 5. The compound of any one of claims 1-4, wherein X is selected from the group consisting of H, OS(=O)2RA, OC(=O)RA, N(C(=O)RA)2, halogen, tetracoordinate boronate, hexacoordinate phosphorus, optionally substituted C6-C10 aryl, and optionally substituted C2-C10 heteroaryl, wherein each optional substituent in the C6-C10 aryl and C2-C8 heteroaryl is independently selected from the group consisting of a halogen, CN, NO2, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C3-C8 cycloalkyl, phenyl, and C2-C8 heterocyclyl 6. The compound of claim 5, wherein X is Cl. 7. The compound of any one of claims 1-6, wherein one of the following applies: (a) Rb1 and Rb2 are each independently selected from the group consisting of H, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, and i-butyl; or (b) Rb1 and Rb2 combine with the nitrogen atom to which they are bound to form a morpholinyl, piperidinyl, fluorenyl, or optionally substituted pyrazolyl. 8. The compound of any one of claims 1-7, wherein Y1 is selected from the group consisting of OMe, NMe2, and NEt2. 9. The compound of any one of claims 1-7, wherein Y1 is selected from the group consisting 10. The compound of any one of claims 1-7, wherein Y2 is selected from the group consisting 11. The compound of any one of claims 3-10, wherein Rc1 and Rc5 are each independently selected from the group consisting of methyl, i-propyl, and diphenylmethyl. 12. The compound of claim 11, wherein Rc1 and Rc5 are identical. 13. The compound of any one of claims 3-12, wherein Rc3 is selected from the group consisting of H and methyl. 14. The compound of any one of claims 3-13, wherein Rc2 and Rc4 are each H. 15. The compound of any one of claims 1-14, wherein Z is selected from the group c 16. The compound of any one of claims 1-15, which is selected from the group consisting of: 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-2-ium chloride; 5-(dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-2-ium chloride; 5-(diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyridin-2-ium chloride; 5-(diethylamino)-2-mesitylimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(diethylamino)imidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-2-ium chloride; 2-mesityl-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-morpholinoimidazo[1,5-a]pyridin-2-ium chloride; 2-mesityl-5-morpholinoimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-morpholinoimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-(3,5-diphenyl-1H-pyrazol-1-yl)imidazo[1,5-a]pyridin-2-ium chloride; 5-(9H-carbazol-9-yl)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-methoxyimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]quinolin-2-ium chloride; 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quinolin-2-ium chloride; 2-(2,6-Diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]quinolin-2-ium chloride; 2-(2,6-Diisopropylphenyl)-9-morpholinoimidazo[1,5-a]quinolin-2-ium chloride; 9-(Dimethylamino)-2-mesitylimidazo[1,5-a]quinolin-2-ium chloride; and 2-(2,6-Diisopropylphenyl)-9-(2,4,6-trimethylphenyl)imidazo[1,5-a]quinolin-2-ium chloride. 17. A method of preparing the compound of formula (Ia) of any one of claims 1-9 and 11-16, the method comprising: contacting a compound of formula (A): a compound of formula (B): paraformaldehyde: , in the presence of an acid to form the compound of formula (Ia). 18. The method of claim 17, wherein the contacting occurs in the presence of a solvent, wherein the solvent is optionally ethanol. 19. The method of claim 17 or 18, wherein the contacting occurs at a temperature ranging from about 40 °C to about 80 °C. 20. The method of any one of claims 17-19, wherein the contacting for a period of time ranging from about 12 to about 36 h. 21. A compound of formula (II) selected from the group consisting of: wherein: M is a transition metal; L is a ligand of M, wherein each occurrence of L can be the same or different; each occurrence of is a single or double bond, wherein no more than one bonding a C atom and a N atom is a double bond; T1 is N or CRa1; T2 is N or CRa2; T3 is N or CRa3; X is a counter anion; Y1, if present, is selected from the group consisting of ORb1 and N(Rb1)(Rb2); Y2, if present, is selected from the group consisting of N(Rb1)(Rb2) and optionally substituted phenyl; Z is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C8 heteroaryl, wherein each optional substituent in Z is independently at least one selected from the group consisting of H, halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, ORA, N(RA)(RB), C(=O)RA, C(=O)N(RA)(RB), C(=O)ORB, N(RA)S(=O)2RB, S(=O)2N(RA), optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C12 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein the C1-C6 alkyl, C3-C8 cycloalkyl, C2-C12 heterocyclyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl are each optionally substituted with at least one substituent selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl; Ra1, Ra2, Ra3, Ra5, and Ra6, if present, are each independently selected from the group consisting of H, halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, ORA, N(RA)(RB), C(=O)RA, C(=O)N(RA)(RB), C(=O)ORB, N(RA)S(=O)2RB, S(=O)2N(RA), optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of Ra1, Ra2, Ra3, Ra5, and Ra6 is independently selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of Ra1, Ra2, Ra3, Ra5, and Ra6 may combine with the carbon atoms to which they are bound to form an optionally substituted C5-C12 cycloalkyl, optionally substituted C2-C12 heterocyclyl, or optionally substituted C6-C10 aryl; Ra4 is selected from the group consisting of H, C1-C6 alkyl, C6-C10 aryl, and C2-C12 heterocyclyl; Rb1 and Rb2 are each independently selected from the group consisting of H, optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein Rb1 and Rb2 may combine with the atom to which they are bound to form an optionally substituted C2-C12 heterocyclyl, wherein each optional substituent in each of Rb1 and Rb2 is independently selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl; RA and RB are each independently selected from the group consisting of H, C1-C6 alkyl, C1-C3 haloalkyl, C2-C6 alkenyl, benzyl, naphthyl, C4-C10 heteroaryl, and phenyl, wherein each substituent in RA and RB is optionally substituted with at least one substituent selected from the group consisting of CN, NO2, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, and halogen; and n is an integer which is selected from the group consisting of 0, 1, 2, and 3. 22. The compound of claim 21, wherein at least one of the following occurs: (a) T1 is CRa1; (b) T2 is CRa2; and (c) T3 is CRa3. 23. The compound of claim 21 or 22, wherein Z is: , wherein: Rc1, Rc2, Rc3, Rc4, and Rc5 are each independently selected from the group consisting of H, halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, ORA, N(RA)(RB), C(=O)RA, C(=O)N(RA)(RB), C(=O)ORB, N(RA)S(=O)2RB, S(=O)2N(RA), optionally substituted C1-C6 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C12 heterocyclyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of Rc1, Rc2, Rc3, Rc4, and Rc5 is independently selected from the group consisting of halogen, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C2-C6 alkenyl, benzyl, phenyl, and naphthyl, and C2-C12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of Rc1, Rc2, Rc3, Rc4, and Rc5 may combine with the carbon atoms to which they are bound to form an optionally substituted C5-C12 cycloalkyl, optionally substituted C2-C12 heterocyclyl, or optionally substituted C6-C10 aryl. 24. The compound of any one of claims 21-23, wherein M is selected from the group consisting of Cu, Ag, Au, Pd, Ni, Pt, Co, Rh, Ir, Fe, Ru, and Os. 25. The compound of claim 24, wherein M is selected from the group consisting of Au, Pd, Rh, Ag and Cu. 26. The compound of any one of claims 21-25, wherein X is selected from the group consisting of H, OS(=O)2RA, OC(=O)RA, N(C(=O)RA)2, halogen, tetracoordinate boronate, hexacoordinate phosphorus, optionally substituted C6-C10 aryl, and optionally substituted C2-C10 heteroaryl, wherein each optional substituent in the C6-C10 aryl and C2-C8 heteroaryl is independently selected from the group consisting of a halogen, CN, NO2, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C3-C8 cycloalkyl, phenyl, and C2-C8 heterocyclyl. 27. The compound of claim 26, wherein X is selected from the group consisting of Cl, trifluoromethanesulfonate (OTf), bis(trifluoromethansulfonyl)amide (NTf2), and allylbenzene anion (i.e., 3-phenylpropen-3-ide and/or 1-phenylpropen-3-ide). 28. The compound of any one of claims 21-27, wherein L is selected from the group consisting of Y1, Y2, carbon monoxide (CO), optionally substituted C2-C12 alkene, and optionally substituted C5-C12 cycloalkene, wherein each optional substituent in the C2-C12 alkene and C5- C12 cycloalkene is independently selected from the group consisting of a halogen, CN, NO2, C1- C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkyl, C3-C8 cycloalkyl, phenyl, and C2-C8 heterocyclyl. 29. The compound of any one of claims 21-27, wherein L is selected from the group consisting of cyclooctadiene (COD) and carbon monoxide (CO). 30. The compound of any one of claims 21-29, wherein at least one of the following occurs: (a) at least one of Ra1, Ra2, and Ra3 is H; (b) at least two of Ra1, Ra2, and Ra3 are H; and (c) each of Ra1, Ra2, and Ra3 are H. 31. The compound of any one of claims 21-30, wherein one of the following applies: (a) Rb1 and Rb2, if present, are each independently selected from the group consisting of H, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, and i-butyl; or (b) Rb1 and Rb2 combine with the nitrogen atom to which they are bound to form a morpholinyl or piperidinyl. 32. The compound of any one of claims 21-31, wherein Y1 is selected from the group consisting of OMe, NMe2, and NEt2. 33. The compound of any one of claims 21-31, wherein Y1 is selected from the group c 34. The compound of any one of claims 21-31, wherein Y2 is selected from the group consisting 35. The compound of any one of claims 23-34, wherein Rc1 and Rc5 are each independently selected from the group consisting of methyl, i-propyl, and diphenylmethyl. 36. The compound of any one of claims 23-35, wherein Rc1 and Rc5 are identical. 37. The compound of any one of claims 23-36, wherein Rc3 is selected from the group consisting of H and methyl. 38. The compound of any one of claims 23-37, wherein Rc2 and Rc4 are each H. 39. The compound of any one of claims 21-38, wherein Z is selected from the group c 40. The compound of any one of claims 21-39, which is selected from the group consisting of: 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 5-(dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 5-(diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 5-(diethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(diethylamino)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-diisopropylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-mesityl-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-diisopropylphenyl)-5-methoxyimidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; cinnamyl[2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridine-3- ylidene]chloropalladium(II); cinnamyl[5-(dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-ylidene]chloropalladium(II); cinnamyl[2-(2,6-dibenzhydryl-4-methylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[5-(diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[5-(diethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-ylidene]chloropalladium(II); cinnamyl[2-(2,6-dibenzhydryl-4-methylphenyl)-5-(diethylamino)imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[2-(2,6-diisopropylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[2-mesityl-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3-ylidene]chloropalladium(II); cinnamyl[2-(2,6-dibenzhydryl-4-methylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[2-(2,6-diisopropylphenyl)-5-morpholinoimidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3-ylidene silver(I) chloride; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3-ylidene copper(I) chloride; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3- ylidene(cyclooctadiene)rhodium(I) chloride; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3- ylidene(cyclooctadiene)rhodium(I) triflate; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3- ylidene(bis(carbonyl))rhodium(I) triflate; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-3-ylidene gold(I) bis(trifluoromethanesulfonyl)amide; 2-(2,6-diisopropylphenyl)-5-(morpholin-4-yl)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,4,6-trimethylphenyl)-5-(morpholin-4-yl)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]quinolin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quinolin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]quinolin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(morpholin -4-yl)imidazo[1,5-a]quinolin-3-ylidene silver(I) chloride; 2-(2,4,6-trimethylphenyl)-9-(dimethylamino)imidazo[1,5-a]quinolin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(morpholin -4-yl)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride; 2-(2,4,6-trimethylphenyl)-9-(dimethylamino)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride; and 2-(2,6-Diisopropylphenyl)-9-(2,4,6-trimethylphenyl)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride. 41. A method of promoting a reaction between a first reagent and an aryl iodide, the method comprising contacting the first reagent and the aryl iodide in the presence of the compound of any one of claims 21-40 and optionally in the presence of a Lewis acid. 42. The method of claim 41, wherein M is Au in the compound of any one of claims 20-38. 43. The method of claim 41 or 42, wherein the compound of any one of claims 20-38 is present in an amount ranging from about 0.1 to about 10 mol%. 44. The method of any one of claims 41-43, wherein the first reagent is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 45. The method of any one of claims 41-44, wherein the aryl iodide is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 46. The method of any one of claims 41-45, wherein the Lewis acid is AgNTf2. 47. The method of any one of claims 41-46, wherein the contacting occurs in the presence of a solvent, wherein the solvent is optionally MeOH. 48. The method of any one of claims 41-47, wherein the contacting occurs at a temperature ranging from about 40 °C to about 80 °C. 49. The method of any one of claims 41-48, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. 50. A method of promoting a reaction between an aniline and an aryl iodide, the method comprising contacting the aniline and the aryl iodide in the presence of the compound of any one of claims 21-40 and optionally in the presence of a Lewis acid. 51. The method of claim 50, wherein M is Au in the compound of any one of claims 21-40. 52. The method of claim 50 or 51, wherein the compound of any one of claims 20-38 is present in an amount ranging from about 0.1 to about 10 mol%. 53. The method of any one of claims 50-52, wherein the aniline is selected from the group consisting of optionally substituted C6-C10 aryl and C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one NH2, and wherein each optional substituent is at least one selected from the group consisting of of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1- C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1- C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 54. The method of any one of claims 50-53, wherein the aryl iodide is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 55. The method of any one of claims 50-54, wherein the Lewis acid is AgNTf2. 56. The method of any one of claims 50-55, wherein the contacting occurs in the presence of a solvent, wherein the solvent is optionally MeOH. 57. The method of any one of claims 50-56, wherein the contacting occurs at a temperature ranging from about 40 °C to about 80 °C. 58. The method of any one of claims 50-57, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. 59. A method of promoting a hydroamination reaction between an alkyne and an amine, the method comprising contacting the alkyne and the amine in the presence of the compound of any one of claims 21-40 and optionally in the presence of a Lewis acid. 60. The method of claim 59, wherein M is Au in the compound of any one of claims 21-40. 61. The method of claim 59 or 60, wherein the compound of any one of claims 21-40 is present in an amount ranging from about 0.1 to about 10 mol%. 62. The method of any one of claims 59-61, wherein the alkyne is selected from the group consisting of optionally substituted C2-C12 alkynyl, optionally substituted C8-C12 aralkynyl, and optionally substituted C4-C12 heteroaralkynyl, wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 63. The method of any one of claims 59-62, wherein the amine is selected from the group consisting of optionally substituted C4-C12 heterocycloalkyl comprising at least one secondary amine, H2N-NH2, H2N-N(optionally substituted C1-C6 alkyl)2, H2N-N(optionally substituted C1- C6 alkyl)(optionally substituted C4-C10 aryl), H2N-N(optionally substituted C4-C10 aryl)2, H2N(optionally substituted C1-C6 alkyl), H2N(optionally substituted C4-C10 aryl), HN(optionally substituted C1-C6 alkyl)(optionally substituted C4-C10 aryl), HN(optionally substituted C4-C10 aryl)2, and NH(optionally substituted C1-C6 alkyl)2, wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1- C6 alkyl, C3-C12 cycloalkyl, C4-C10 heterocycloalkyl, C2-C6 alkenyl, phenyl, naphthyl, C4-C10 heteroaryl, N(C1-C6 alkyl)2, halogen, CN, NO2, C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 64. The method of any one of claims 59-63, wherein the Lewis acid is sodium tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (NaBArF). 65. The method of any one of claims 59-64, wherein the contacting occurs in the presence of a solvent. 66. The method of claim 65, wherein the solvent is toluene. 67. The method of any one of claims 59-66, wherein the contacting occurs at a temperature ranging from about 90 °C to about 110 °C. 68. The method of any one of claims 59-67, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. 69. The method of any one of claims 59-68, wherein the contacting of the alkyne and amine provides an imine intermediate. 70. The method of claim 69, wherein a reduction reaction is promoted by contacting the imine intermediate and a reducing agent. 71. The method of claim 70, wherein the reducing agent is sodium triacetoxyborohydride (NaBH(OAc)3). 72. A method of promoting hydration of an alkyne, the method comprising contacting the alkyne and water in the presence of the compound of any one of claims 21-40 and optionally in the presence of a Lewis acid. 73. The method of claim 72, wherein M is Au in the compound of any one of claims 21-40. 74. The method of claim 72 or 73, wherein the compound of any one of claims 21-40 is present in an amount ranging from about 0.01 to about 1 mol%. 75. The method of any one of claims 72-74, wherein the alkyne is selected from the group consisting of optionally substituted C2-C12 alkynyl, optionally substituted C8-C12 aralkynyl, and optionally substituted C4-C12 heteroaralkynyl, wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 76. The method of any one of claims 72-75, wherein the Lewis acid is AgSbF6. 77. The method of any one of claims 72-76, wherein the contacting occurs in the presence of a solvent. 78. The method of claim 77, wherein the solvent is a mixture of 1,4-dioxane and water. 79. The method of claim 78, wherein the mixture of 1,4-dioxane and water has a ratio of about 10 : 1 to about 0.1 : 1 (1,4-dioxane : water). 80. The method of any one of claims 72-79, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. 81. The method of any one of claims 72-80, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. 82. A method of promoting a reaction between an aryl chloride and a lithium amide, the method comprising contacting the aryl chloride and the lithium amide in the presence of the compound of any one of claims 21-40. 83. The method of claim 82, wherein M is Pd in the compound of any one of claims 21-40. 84. The method of claim 82 or 83, wherein the compound of any one of claims 21-40 is present in an amount ranging from about 0.1 to about 10 mol%. 85. The method of any one of claims 82-84, wherein the lithium amide is prepared by contacting an amine with a second lithium amide. 86. The method of claim 85, wherein the second lithium amide is lithium hexamethyldisilazide (LiHMDS). 87. The method of claim 85 or 86, wherein the amine is selected from the group consisting of optionally substituted C4-C12 heterocycloalkyl comprising at least one secondary amine, H2N- NH2, H2N-N(optionally substituted C1-C6 alkyl)2, H2N-N(optionally substituted C1-C6 alkyl)(optionally substituted C4-C10 aryl), H2N-N(optionally substituted C4-C10 aryl)2, H2N(optionally substituted C1-C6 alkyl), H2N(optionally substituted C4-C10 aryl), HN(optionally substituted C1-C6 alkyl)(optionally substituted C4-C10 aryl), HN(optionally substituted C4-C10 aryl)2, and NH(optionally substituted C1-C6 alkyl)2, wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1- C6 alkyl, C3-C12 cycloalkyl, C4-C10 heterocycloalkyl, C2-C6 alkenyl, phenyl, naphthyl, C4-C10 heteroaryl, N(C1-C6 alkyl)2, halogen, CN, NO2, C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 88. The method of any one of claims 82-87, wherein the aryl chloride is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one chlorine atom, and wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 89. The method of any one of claims 82-88, wherein the contacting occurs in the presence of a solvent. 90. The method of claim 89, wherein the solvent is 1,4-dioxane. 91. The method of any one of claims 82-90, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. 92. The method of any one of claims 82-91, wherein the contacting occurs for a period of time ranging from about 12 to about 24 h. 93. A method of promoting a reaction between an aryl chloride and an arylmagnesium halide, the method comprising contacting the aryl chloride and the arylmagnesium halide in the presence of the compound of any one of claims 21-40. 94. The method of claim 93, wherein M is Pd in the compound of any one of claims 21-40. 95. The method of claim 93 or 94, wherein the compound of any one of claims 21-40 has a concentration of about 0.1 to about 10 mol%. 96. The method of any one of claims 93-95, wherein the aryl chloride is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one chlorine atom, and wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, N(C1-C6 alkyl)2, halogen, and NO2. 97. The method of any one of claims 93-96, wherein the arylmagnesium halide is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with a magnesium halide moiety, and wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, N(C1-C6 alkyl)2, halogen, and NO2. 98. The method of any one of claims 93-97, wherein the contacting occurs in the presence of a solvent. 99. The method of claim 98, wherein the solvent is 1,4-dioxane. 100. The method of any one of claims 93-99, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. 101. The method of any one of claims 93-100, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. 102. A method of promoting a reaction between an aroyl chloride and an aryl boronic acid, the method comprising contacting the aroyl chloride and the aryl boronic acid in the presence of the compound of any one of claims 21-40 and a base. 103. The method of claim 102, wherein M is Pd in the compound of any one of claims 21-40. 104. The method of claim 102 or 103, wherein the compound of any one of claims 21-40 is present in an amount ranging from about 0.1 to about 10 mol%. 105. The method of any one of claims 102-104, wherein the aroyl chloride is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with a C(=O)Cl moiety, and wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, N(C1-C6 alkyl)2, halogen, CN, NO2, C(=O)O(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 106. The method of any one of claims 102-105, wherein the aryl boronic acid is selected from the group consisting of optionally substituted C6-C10 aryl boronic acid and optionally substituted C4-C10 heteroaryl boronic acid, wherein each optional substituent is at least one selected the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 107. The method of any one of claims 102-106, wherein the base is K2CO3. 108. The method of any one of claims 102-107, wherein the reaction occurs in the presence of a solvent. 109. The method of claim 108, wherein the solvent is 1,4-dioxane. 110. The method of any one of claims 102-109, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. 111. The method of any one of claims 102-110, wherein the contacting occurs for a period of time ranging from about 8 h to about 24 h. 112. A method of promoting a reaction between an aryl iodide, an aniline, and carbon monoxide (CO), the method comprising contacting the aryl iodide, the aniline, and the CO in the presence of the compound of any one of claims 21-40 and a base. 113. The method of claim 112, wherein M is Pd in the compound of any one of claims 21-40. 114. The method of claim 112 or 113, wherein the compound of any one of claims 21-40 is present in an amount ranging from about 0.1 to about 10.0 mol%. 115. The method of any one of claims 112-114, wherein the aryl iodide is selected from the group consisting of optionally substituted C6-C10 aryl and optionally substituted C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1-C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1-C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 116. The method of any one of claims 112-115, wherein the aniline is selected from the group consisting of optionally substituted C6-C10 aryl and C2-C10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one NH2, and wherein each optional substituent is at least one selected from the group consisting of of C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6, haloalkyl, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocyclyl, C2-C6 alkenyl, phenyl, naphthyl, NH2, N(C1- C6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C1-C6 alkyl), C(=O)NH2, C(=O)NH(C1- C6 alkyl), and C(=O)N(C1-C6 alkyl)2. 117. The method of any one of claims 112-116, wherein the CO has a pressure ranging from about 0.1 to about 10 atm. 118. The method of any one of claims 112-117, wherein the base is K3PO4. 119. The method of any one of claims 112-118, wherein the contacting occurs in the presence of a solvent. 120. The method of claim 119, wherein the solvent is toluene. 121. The method of any one of claims 112-120, wherein the contacting occurs at a temperature ranging from about 90 °C to about 110 °C. 122. The method of any one of claims 112-121, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. 123. A method of preparing 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5- a]pyridin-2-ium chloride) (1): the method comprising reacting (E)-6-(((2,6-diisopropylphenyl)imino)methyl)-N,N- dimethylpyridin-2-amine (A): and paraformaldehyde so as to generate a first reaction system comprising (1). 124. The method of claim 123, wherein the reaction of (Z) and paraformaldehyde is performed in the presence of a solvent. 125. The method of claim 124, wherein the solvent is EtOH. 126. The method of any one of claims 123-125, further comprising hydrochloric acid (HCl). 127. The method of any one of claims 123-126, wherein the reaction of (Z) and paraformaldehyde is performed at a temperature of about 70 °C. 128. The method of any one of claims 123-127, wherein the (Z) is prepared by reacting 6- (dimethylamino)picolinaldehyde (Y): and 2,6-diisopropylaniline (X): 129. The method of claim 128, wherein the reaction of (Y) and (X) is performed in the presence of a solvent. 130 The method of claim 129 wherein the solvent is EtOH 131. The method of any one of claims 128-130, wherein the reaction of (Y) and (X) is performed at a temperature of about 90 °C. 132. The method of any one of claims 128-131, wherein the (Y) is prepared by reacting 6- bromo-N,N-dimethylpyridin-2-amine (W): and an organolithium reagent to form a lithiated intermediate, and contacting the lithiated intermediate with a formylating reagent. 133. The method of claim 132, wherein the reaction of (W) and the organolithium reagent is performed in the presence of a solvent. 134. The method of claim 133, wherein the solvent is tetrahydrofuran (THF). 135. The method of any one of claims 132-134, wherein the organolithium reagent is n- butyllithium (n-BuLi). 136. The method of any one of claims 132-135, wherein the reaction of (W) and the organolithium reagent is performed at about -78 °C. 137. The method of any one of claims 132-136, wherein the reaction of the lithiated intermediate and the formylating reagent is performed in the presence of a solvent. 138. The method of claim 137, wherein the solvent is tetrahydrofuran (THF). 139. The method of any one of claims 132-138, wherein the formylating agent is dimethylformamide (DMF). 140. The method of any one of claims 132-139, wherein the contacting occurs at a temperature of about -78 °C. 141. The method of any one of claims 132-136, wherein the (W) is prepared by reacting (V): and dimethylamine (HNMe2), in the presence of a base. 142. The method of claim 141, wherein the reaction of (V) and dimethylamine is performed in the presence of a solvent. 143. The method of claim 142, wherein the solvent is acetonitrile (ACN). 144. The method of any one of claims 141-143, wherein the base is K2CO3. 145. The method of any one of claims 141-144, wherein the reaction of (V) and dimethylamine is performed at a temperature of about 100 °C. |
Methods Ligand Synthesis The present disclosure further provides a method of preparing the compound formula (Ia), the method comprising: contacting a compound of formula (A): T T a compound of formula (B): (B), and formaldehyde in the presence of an acid to form the compound of formula (Ia). In certain embodiments, the formaldehyde is paraformaldehyde: In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is ethanol. In certain embodiments, the contacting occurs at room temperature. In certain embodiments, the temperature of contacting is elevated to a second temperature selected from the group consisting of about 40, 45, 50, 55, 60, 65, 70, 75, and about 80 °C. In certain embodiments, the contacting for a period of time selected from the group consisting of about 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, and about 36 h. The present disclosure further provides a method of preparing 2-(2,6-Diisopropylphenyl)- 5-(dimethylamino)imidazo[1,5-a]pyridin-2-ium chloride) (1): the method comprising reacting (E)-6-(((2,6-diisopropylphenyl)imino)methyl)-N,N- dimethylpyridin-2-amine (Z): and paraformaldehyde so as to generate a first reaction system comprising (1). In certain embodiments, the reaction of (Z) and paraformaldehyde is performed in the presence of a solvent. In certain embodiments, the solvent is EtOH. In certain embodiments, the reaction further comprises hydrochloric acid (HCl). In certain embodiments, the reaction of (Z) and paraformaldehyde is performed at a temperature selected from the group consisting of about 50, 55, 60, 65, 70, 75, 80, 85, and 90 °C. In certain embodiments, the (Z) is prepared by reacting 6- (dimethylamino)picolinaldehyde (Y): and 2,6-diisopropylaniline (X): In certain embodiments, the reaction of (Y) and (X) is performed in the presence of a solvent. In certain embodiments, the solvent is EtOH. In certain embodiments, the reaction of (Y) and (X) is performed at a temperature selected from the group consisting of about 70, 75, 80, 85, 90, 95, and 100 °C. In certain embodiments, the (Y) is prepared by reacting 6-bromo-N,N-dimethylpyridin-2- amine (D): and an organolithium reagent to form a lithiated intermediate, and contacting the lithiated intermediate with a formylating reagent. In certain embodiments, the reaction of (W) and the organolithium reagent is performed in the presence of a solvent. In certain embodiments, the solvent is tetrahydrofuran (THF). In certain embodiments, the organolithium reagent is selected from the group consisting of n-butyllithium (n-BuLi), sec-butyllithium (s-BuLi), t-butyllithium (t-BuLi), and phenyllithium (PhLi). In certain embodiments, the reaction of (W) and the organolithium reagent is performed at about -78 °C. In certain embodiments, the reaction of the lithiated intermediate and the formylating reagent is performed in the presence of a solvent. In certain embodiments, the solvent is tetrahydrofuran (THF). In certain embodiments, the formylating agent is dimethylformamide (DMF). In certain embodiments, the contacting occurs at a temperature of about -78 °C. In certain embodiments, the (W) is prepared by reacting (V): and dimethylamine (HNMe2), in the presence of a base. In certain embodiments, the reaction of (V) and dimethylamine is performed in the presence of a solvent. In certain embodiments, the solvent is acetonitrile (ACN). In certain embodiments, the base is K 2 CO 3 . In certain embodiments, the reaction of (V) and dimethylamine is performed at a temperature selected from the group consisting of about 80, 85, 90, 95, 100, 105, 110, 115, and 120 °C. Catalysis The present disclosure provides a method of promoting a reaction (coupling) between a first reagent and an aryl iodide (i.e., promoting arylation of a first reagent). In certain embodiments, the method comprises contacting the first reagent and the aryl iodide in the presence of the N-heterocyclic carbene complex of the present disclosure. In certain embodiments, the contacting occurs in the presence of a Lewis acid. In certain embodiments, M is Au in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount selected from the group consisting of about 0.1, 0.20.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2.1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7.6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, and about 10 mol%. In certain embodiments, the first reagent is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . In certain embodiments, the aryl iodide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . In certain embodiments, the Lewis acid is AgNTf2. In certain embodiments, the Lewis acid is sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr F ). In certain embodiments, the Lewis acid is AgSbF 6 . In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is MeOH. In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 40, 45, 50, 55, 60, 65, 70, 75, and about 80 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24 h. The present disclosure further provides a method of promoting a reaction (coupling) between an aniline and an aryl iodide (i.e., promoting arylation of an aniline), the method comprising contacting the aniline and the aryl iodide in the presence of the NHC complex of the present disclosure. In certain embodiments, the contacting occurs in the presence of a Lewis acid. In certain embodiments, M is Au in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount selected from the group consisting of about 0.1, 0.20.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2.1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7.6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, and about 10 mol%. In certain embodiments, the aniline is selected from the group consisting of optionally substituted C 6 -C 10 aryl and C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one NH 2 , and wherein each optional substituent is at least one selected from the group consisting of of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . In certain embodiments, the aryl iodide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the Lewis acid is AgNTf2. In certain embodiments, the Lewis acid is sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr F ). In certain embodiments, the Lewis acid is AgSbF 6 . In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is MeOH. In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 40, 45, 50, 55, 60, 65, 70, 75, and about 80 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24 h. The present disclosure further provides a method of promoting a hydroamination reaction between an alkyne and an amine, the method comprising contacting the alkyne and the amine in the presence of the NHC complex of the present disclosure. In certain embodiments, the contacting occurs in the presence of a Lewis acid. In certain embodiments, M is Au in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount selected from the group consisting of about 0.1, 0.20.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2.1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7.6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, and about 10 mol%. In certain embodiments, the alkyne is selected from the group consisting of optionally substituted C 2 -C 12 alkynyl, optionally substituted C 8 -C 12 aralkynyl, and optionally substituted C 4 - C 12 heteroaralkynyl, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH2, C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the amine is selected from the group consisting of optionally substituted C4-C 12 heterocycloalkyl comprising at least one secondary amine, H2N-NH2, H2N- N(optionally substituted C 1 -C 6 alkyl)2, H2N-N(optionally substituted C 1 -C 6 alkyl)(optionally substituted C 4 -C 10 aryl), H 2 N-N(optionally substituted C 4 -C 10 aryl) 2 , H 2 N(optionally substituted C 1 -C 6 alkyl), H 2 N(optionally substituted C 4 -C 10 aryl), HN(optionally substituted C 1 -C 6 alkyl)(optionally substituted C4-C 10 aryl), HN(optionally substituted C4-C 10 aryl)2, and NH(optionally substituted C 1 -C 6 alkyl) 2 , wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 - C 12 cycloalkyl, C4-C 10 heterocycloalkyl, C 2 -C 6 alkenyl, phenyl, naphthyl, C4-C 10 heteroaryl, N(C 1 -C 6 alkyl) 2 , halogen, CN, NO 2, C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . In certain embodiments, the Lewis acid is AgNTf2. In certain embodiments, the Lewis acid is sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr F ). In certain embodiments, the Lewis acid is AgSbF 6 . In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is toluene. In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, and about 110 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24 h. In certain embodiments, the contacting of the alkyne and amine provides an imine intermediate. In certain embodiments, a reduction reaction is promoted by contacting the imine intermediate and a reducing agent. In certain embodiments, the reducing agent is sodium triacetoxyborohydride (NaBH(OAc) 3 ). The present disclosure further provides method of promoting hydration of an alkyne, the method comprising contacting the alkyne and water in the presence of the NHC complex of the present disclosure. In certain embodiments, the contacting occurs in the presence of a Lewis acid. In certain embodiments, M is Au in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount selected from the group consisting of about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99 and about 1 mol%. In certain embodiments, the alkyne is selected from the group consisting of optionally substituted C 2 -C 12 alkynyl, optionally substituted C 8 -C 12 aralkynyl, and optionally substituted C 4 - C 12 heteroaralkynyl, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the Lewis acid is AgNTf2. In certain embodiments, the Lewis acid is sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr F ). In certain embodiments, the Lewis acid is AgSbF 6 . In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is a mixture of 1,4-dioxane and water. In certain embodiments, the mixture of 1,4-dioxane and water has a ratio selected from the group consisting of about 10 : 1, 9 : 1, 8 : 1, 7 : 1, 6 : 1, 5 : 1, 4 : 1, 3 : 1, 2 : 1, 1 : 1, 0.9 : 1, 0.8 : 1, 0.7 : 1, 0.6 : 1, 0.5 : 1, 0.4 : 1, 0.3 : 1, 0.2 : 1, and about 0.1 : 1 (1,4-dioxane : water). In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 and about 100 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24. The present disclosure further provides a method of promoting a reaction (coupling) between an aryl chloride and a lithium amide (i.e., promoting arylation of an amide), the method comprising contacting the aryl chloride and the lithium amide in the presence of the NHC complex of the present disclosure. In certain embodiments, M is Pd in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount selected from the group consisting of about 0.1, 0.20.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2.1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7.6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, and about 10 mol%. In certain embodiments, the lithium amide is prepared by contacting an amine with a second lithium amide. In certain embodiments, the second lithium amide is lithium hexamethyldisilazide (LiHMDS). In certain embodiments, the amine is selected from the group consisting of optionally substituted C4-C 12 heterocycloalkyl comprising at least one secondary amine, H2N-NH2, H2N- N(optionally substituted C 1 -C 6 alkyl)2, H2N-N(optionally substituted C 1 -C 6 alkyl)(optionally substituted C 4 -C 10 aryl), H 2 N-N(optionally substituted C 4 -C 10 aryl) 2 , H 2 N(optionally substituted C 1 -C 6 alkyl), H 2 N(optionally substituted C 4 -C 10 aryl), HN(optionally substituted C 1 -C 6 alkyl)(optionally substituted C4-C 10 aryl), HN(optionally substituted C4-C 10 aryl)2, and NH(optionally substituted C 1 -C 6 alkyl)2, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 - C 12 cycloalkyl, C 4 -C 10 heterocycloalkyl, C 2 -C 6 alkenyl, phenyl, naphthyl, C 4 -C 10 heteroaryl, N(C 1 -C 6 alkyl)2, halogen, CN, NO2, C(=O)NH2, C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the aryl chloride is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one chlorine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH2, C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is 1,4-dioxane. In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 and about 100 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24 h. The present disclosure further provides a method of promoting a reaction (coupling) between an aryl chloride and an arylmagnesium halide, the method comprising contacting the aryl chloride and the arylmagnesium halide in the presence of the NHC complex of the present disclosure. In certain embodiments, M is Pd in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount selected from the group consisting of about 0.1, 0.20.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2.1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7.6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, and about 10 mol%. In certain embodiments, the aryl chloride is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one chlorine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, N(C 1 -C 6 alkyl)2, halogen, and NO2. In certain embodiments, the arylmagnesium halide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with a magnesium halide moiety, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, N(C 1 -C 6 alkyl)2, halogen, and NO2. In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is 1,4-dioxane. In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 and about 100 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24 h. The present disclosure further provides a method of promoting a reaction (coupling) between an aroyl chloride and an aryl boronic acid (i.e., promoting aroylation of an aryl reagent), the method comprising contacting the aroyl chloride and the aryl boronic acid in the presence of the NHC complex of the present disclosure and a base. In certain embodiments, M is Pd in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount ranging from about 0.1 to about 10 mol%. In certain embodiments, the aroyl chloride is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with a C(=O)Cl moiety, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, N(C 1 -C 6 alkyl)2, halogen, CN, NO2, C(=O)O(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the aryl boronic acid is selected from the group consisting of optionally substituted C 6 -C 10 aryl boronic acid and optionally substituted C 4 -C 10 heteroaryl boronic acid, wherein each optional substituent is at least one selected the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the base is K2CO3. In certain embodiments, the reaction occurs in the presence of a solvent. In certain embodiments, the solvent is 1,4-dioxane. In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 and about 100 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24 h. The present disclosure further provides a method of promoting a reaction between an aryl iodide, an aniline, and carbon monoxide (CO), the method comprising contacting the aryl iodide, the aniline, and the CO in the presence of the NHC complex of the present disclosure and a base. In certain embodiments, M is Pd in the NHC complex of the present disclosure. In certain embodiments, the NHC complex of the present disclosure is present in an amount selected from the group consisting of about 0.1, 0.20.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2.1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7.6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, and about 10 mol%. In certain embodiments, the aryl iodide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . In certain embodiments, the aniline is selected from the group consisting of optionally substituted C 6 -C 10 aryl and C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one NH 2 , and wherein each optional substituent is at least one selected from the group consisting of of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. In certain embodiments, the CO has a pressure selected from the group consisting of about 0.1, 0.20.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2.1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7.6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, and about 10 atm. In certain embodiments, the base is K3PO4. In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is toluene. In certain embodiments, the contacting occurs at a temperature selected from the group consisting of about 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, and about 110 °C. In certain embodiments, the contacting occurs for a period of time selected from the group consisting of about 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and about 24 h. Examples Various embodiments of the present application can be better understood by reference to the following Examples which are offered by way of illustration. The scope of the present application is not limited to the Examples given herein. Example 1: Synthesis of Imidazo[1,5-α]pyridine N-Heterocyclic Carbene (NHC) Ligands Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-2-ium chloride (1) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(dimethylamino)picolinaldehyde (1.5 g, 10 mmol, 1.0 equiv), 2,6-diisopropylaniline (1.77 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M, dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction mixture was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (3.08 g, 86%). 1 H NMR (500 MHz, CDCl3) δ 9.85 (s, 1H), 8.41 (d, J = 1.5 Hz, 1H), 8.02 (d, J = 9.2 Hz, 1H), 7.57 (t, J = 7.9 Hz, 1H), 7.38 (dd, J = 9.1, 7.5 Hz, 1H), 7.34 (d, J = 7.9 Hz, 2H), 6.70 (d, J = 7.3 Hz, 1H), 3.00 (s, 6H), 2.15 (dt, J = 13.6, 6.8 Hz, 2H), 1.22 (d, J = 6.8 Hz, 6H), 1.19 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 144.99, 144.18, 132.38, 132.05, 130.82, 127.30, 124.58, 124.03, 117.22, 113.57, 105.10, 41.98, 28.78, 24.62, 24.28. HRMS calcd for C 2 1H28N3 + (M – Cl-) 322.2278, found 322.2281. S An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6 (dimethylamino)picolinaldehyde (15 g 10 mmol 10 equiv) 246 trimethylaniline (135 g 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH2Cl2/MeOH = 20/1) to afford the title product (2.65 g, 84%). 1 H NMR (500 MHz, CDCl3) δ 10.23 (s, 1H), 8.21 (d, J = 1.7 Hz, 1H), 7.82 (d, J = 9.2 Hz, 1H), 7.31 (dd, J = 6.9, 2.3 Hz, 1H), 7.04 (s, 2H), 6.61 (d, J = 7.1 Hz, 1H), 3.02 (s, 6H), 2.35 (s, 3H), 2.08 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 144.50, 141.27, 133.95, 132.31, 131.40, 129.79, 126.87, 124.53, 115.57, 112.78, 104.31, 42.07, 21.17, 17.66. HRMS calcd for C 18 H 22 N 3 + (M – Cl-) 280.1808, found 280.1810. Synthesis of 2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(dimethylamino)imidazo [1,5-a]pyridin-2- ium chloride (3) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(dimethylamino)picolinaldehyde (1.5 g, 10 mmol, 1.0 equiv), 2,6-dibenzhydryl-4- methylaniline (4.40 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (4.83 g, 78%). 1 H NMR (500 MHz, CDCl 3 ) δ 8.66 (s, 1H), 7.89 (s, 1H), 7.66 (s, 1H), 7.27 – 7.13 (m, 13H), 7.04 (d, J = 7.0 Hz, 4H), 6.88 (d, J = 6.7 Hz, 4H), 6.78 (s, 2H), 6.43 (d, J = 6.6 Hz, 1H), 5.26 (s, 2H), 2.36 (s, 6H), 2.23 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 142.39, 141.26, 140.40, 140.35, 139.87, 130.40, 130.06, 129.53, 128.56, 127.84, 127.61, 127.57, 125.96, 125.88, 125.00, 124.01, 116.08, 112.32, 102.72, 50.69, 40.29, 20.90. HRMS calcd for C42H38N3 + (M – Cl-) 584.3060, found 584.3049. An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-bromo-N,N-diethylpyridin-2-amine (4.58 g, 20 mmol, 1.0 equiv) and dry THF (35 mL). n- BuLi (1.6 M in hexane, 15 mL, 1.2 equiv) was added dropwise at -78 °C and the resulting mixture was stirred at -78 °C for 1 hour. After the indicated time, DMF (1.86 mL, 24 mmol, 1.2 equiv) was added dropwise at -78 °C and the reaction mixture was stirred for 1 hour at -78 °C. After the indicated time, the reaction mixture was diluted with EtOAc (50 mL), washed with H 2 O (1 x 20 mL) and brine (1 x 20 mL). The organic layers were combined, dried with Na 2 SO 4 , filtered, and concentrated. The residue was purified by chromatography on silica gel to afford the title product (3.1 g, 87%). Colorless oil. 1 H NMR (500 MHz, CDCl3) δ 9.79 (s, 1H), 7.48 – 7.40 (m, 1H), 7.06 (d, J = 7.2 Hz, 1H), 6.56 (d, J = 8.6 Hz, 1H), 3.48 (q, J = 7.1 Hz, 4H), 1.11 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 194.85, 157.61, 151.50, 137.56, 110.01, 109.18, 42.48, 12.84. HRMS calcd for C 10 H15N2O + (M + H + ) 179.1179, found 179.1141. Synthesis of 5-(Diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyri din-2-ium chloride (4) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(diethylamino)picolinaldehyde (1.78 g, 10 mmol, 1.0 equiv), 2,6-diisopropylaniline (1.77 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH2Cl2/MeOH = 20/1) to afford the title product (2.93 g, 76%). 1 H NMR (500 MHz, CDCl3) δ 9.14 (s, 1H), 8.86 (s, 1H), 8.44 (d, J = 9.4 Hz, 1H), 7.60 (t, J = 7.9 Hz, 1H), 7.47 – 7.40 (m, 1H), 7.36 (d, J = 7.9 Hz, 2H), 6.84 (d, J = 7.3 Hz, 1H), 3.25 (q, J = 7.1 Hz, 4H), 2.16 (dt, J = 13.6, 6.7 Hz, 2H), 1.24 (d, J = 6.8 Hz, 6H), 1.18 (d, J = 6.9 Hz, 6H), 1.14 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 145.04, 141.08, 132.84, 132.12, 130.82, 126.71, 124.65, 122.23, 118.91, 116.42, 110.26, 45.89, 28.76, 24.73, 24.08, 11.94. HRMS calcd for C 2 3H32N3 + (M – Cl-) 350.2591, found 350.2594. An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(diethylamino)picolinaldehyde (1.78 g, 10 mmol, 1.0 equiv), 2,4,6-trimethylaniline (1.35 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (2.75 g, 80%). 1 H NMR (500 MHz, CDCl 3 ) δ 9.54 (s, 1H), 8.49 (d, J = 1.6 Hz, 1H), 8.07 (d, J = 9.2 Hz, 1H), 7.35 (t, J = 8.2 Hz, 1H), 7.04 (s, 2H), 6.74 (d, J = 7.2 Hz, 1H), 3.29 (q, J = 7.1 Hz, 4H), 2.35 (s, 3H), 2.06 (s, 6H), 1.13 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 141.25, 141.03, 133.69, 132.39, 131.19, 129.57, 126.32, 122.79, 116.65, 114.61, 109.21, 45.11, 20.97, 17.41, 11.46. HRMS calcd for C 20 H 26 N 3 + (M – Cl-) 308.2121, found 308.2126. Synthesis of 2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(diethylamino)imidazo[ 1,5-a]pyridin-2-ium chloride (6) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(diethylamino)picolinaldehyde (1.78 g, 10 mmol, 1.0 equiv), 2,6-dibenzhydryl-4-methylaniline (4.40 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (4.54 g, 70%). 1 H NMR (500 MHz, CDCl3) δ 9.12 (d, J = 1.3 Hz, 1H), 8.14 (d, J = 9.2 Hz, 1H), 7.46 (s, 1H), 7.25 – 7.11 (m, 13H), 7.02 (d, J = 7.3 Hz, 4H), 6.90 – 6.81 (m, 4H), 6.77 (s, 2H), 6.38 (d, J = 7.1 Hz, 1H), 5.25 (s, 2H), 2.52 (q, J = 7.0 Hz, 4H), 2.22 (s, 3H), 0.82 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 142.36, 141.47, 141.32, 140.62, 140.31, 131.99, 131.03, 130.66, 129.69, 128.69, 128.59, 128.53, 127.09, 126.99, 125.77, 123.42, 118.22, 114.99, 107.78, 51.62, 43.57, 21.90, 11.27. HRMS calcd for C 44 H 42 N 3 + (M – Cl-) 612.3373, found 612.3354. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]py ridin-2-ium chloride (7) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(piperidin-1-yl)picolinaldehyde (1.9 g, 10 mmol, 1.0 equiv), 2,6-diisopropylaniline (1.77 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (2.98 g, 75%). 1 H NMR (500 MHz, CDCl 3 ) δ 8.89 (s, 1H), 8.82 (d, J = 1.4 Hz, 1H), 8.34 (d, J = 9.2 Hz, 1H), 7.59 (t, J = 7.9 Hz, 1H), 7.44 – 7.27 (m, 3H), 6.77 (d, J = 7.3 Hz, 1H), 3.19 – 3.03 (m, 4H), 2.15 (dd, J = 13.6, 6.8 Hz, 2H), 1.88 – 1.76 (m, 4H), 1.70 (d, J = 4.8 Hz, 2H), 1.22 (d, J = 6.8 Hz, 6H), 1.18 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 145.04, 143.28, 132.61, 132.14, 130.79, 127.16, 124.71, 121.43, 118.84, 115.64, 106.72, 51.64, 28.75, 25.61, 24.75, 24.25, 23.83. HRMS calcd for C 2 4H32N3 + (M – Cl-) 362.2591, found 362.2596. An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(piperidin-1-yl)picolinaldehyde (1.9 g, 10 mmol, 1.0 equiv), 2,4,6-trimethylaniline (1.35 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (2.56 g, 72%). 1 H NMR (500 MHz, CDCl 3 ) δ 9.47 (s, 1H), 8.47 (s, 1H), 8.01 (d, J = 9.0 Hz, 1H), 7.31 (t, J = 8.0 Hz, 1H), 7.04 (s, 2H), 6.66 (d, J = 7.1 Hz, 1H), 3.14 (s, 4H), 2.35 (s, 3H), 2.06 (s, 6H), 1.86 (s, 4H), 1.68 (s, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 143.66, 141.04, 133.80, 132.23, 131.20, 129.54, 126.74, 122.24, 116.56, 114.02, 105.83, 51.45, 25.27, 23.70, 20.99, 17.47. HRMS calcd for C 21 H 26 N 3 + (M – Cl-) 320.2121, found 320.2121. Synthesis of 2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(piperidin-1-yl)imidaz o[1,5-a]pyridin-2-ium chloride (9) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(piperidin-1-yl)picolinaldehyde (1.9 g, 10 mmol, 1.0 equiv), 2,6-dibenzhydryl-4-methylaniline (4.40 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (4.49 g, 68%). 1 H NMR (500 MHz, CDCl3) δ 9.43 (s, 1H), 8.26 (d, J = 9.2 Hz, 1H), 7.20 (dq, J = 22.4, 7.2 Hz, 7H), 7.14 – 7.07 (m, 6H), 7.02 (d, J = 7.4 Hz, 4H), 6.75 (dd, J = 12.8, 7.8 Hz, 7H), 6.38 (d, J = 7.2 Hz, 1H), 5.15 (s, 2H), 2.37 – 2.26 (m, 4H), 2.22 (s, 3H), 1.47 (s, 2H), 1.29 (s, 4H). 13 C NMR (126 MHz, CDCl3) δ 142.56, 142.44, 141.59, 141.08, 140.76, 131.95, 130.98, 130.57, 129.75, 128.66, 128.59, 128.32, 127.31, 127.02, 126.20, 122.91, 118.10, 115.29, 105.46, 51.58, 50.85, 25.40, 23.63, 21.90. HRMS calcd for C 45 H 42 N 3 + (M – Cl-) 624.3373, found 624.3353. An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-morpholinopicolinaldehyde (1.92 g, 10 mmol, 1.0 equiv), 2,6-diisopropylaniline (1.77 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (2.8 g, 70%). 1 H NMR (500 MHz, CDCl 3 ) δ 10.28 (d, J = 0.8 Hz, 1H), 8.29 (d, J = 1.6 Hz, 1H), 7.99 (d, J = 9.2 Hz, 1H), 7.54 (t, J = 7.8 Hz, 1H), 7.43 – 7.34 (m, 1H), 7.31 (d, J = 7.9 Hz, 2H), 6.80 (d, J = 7.2 Hz, 1H), 4.05 – 3.94 (m, 4H), 3.25 – 3.14 (m, 4H), 2.11 (dt, J = 13.6, 6.8 Hz, 2H), 1.21 (d, J = 6.8 Hz, 6H), 1.14 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 144.79, 142.87, 131.94, 131.88, 130.82, 127.11, 124.42, 117.24, 114.59, 106.33, 66.23, 50.51, 28.68, 24.43, 24.31. HRMS calcd for C 2 3H30N3O + (M – Cl-) 364.2383, found 364.2386. An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-morpholinopicolinaldehyde (1.92 g, 10 mmol, 1.0 equiv), 2,4,6-trimethylaniline (1.35 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (2.79 g, 78%). 1 H NMR (500 MHz, CDCl 3 ) δ 10.70 (s, 1H), 7.94 (s, 1H), 7.72 (d, J = 9.1 Hz, 1H), 7.25 (d, J = 7.9 Hz, 1H), 6.96 (s, 2H), 6.60 (d, J = 7.1 Hz, 1H), 4.01 (s, 4H), 3.18 (s, 4H), 2.27 (s, 3H), 2.02 (s, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 143.62, 141.16, 134.02, 131.95, 131.45, 129.74, 126.67, 125.53, 115.41, 113.78, 105.31, 66.37, 50.68, 21.19, 17.80. HRMS calcd for C 2 0H24N3O + (M – Cl-) 322.1914, found 322.1917. Synthesis of 2-(2,6-Dibenzhydryl-4-methylphenyl)-5-morpholinoimidazo[1,5- a]pyridin-2-ium chloride (12) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-morpholinopicolinaldehyde (1.92 g, 10 mmol, 1.0 equiv), 2,6-dibenzhydryl-4-methylaniline (4.40 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (4.30 g, 65%). 1 H NMR (500 MHz, CDCl3) δ 8.96 (d, J = 1.4 Hz, 1H), 8.15 (d, J = 9.2 Hz, 1H), 7.55 (s, 1H), 7.30 – 7.10 (m, 13H), 7.02 (d, J = 7.2 Hz, 4H), 6.88 (d, J = 6.4 Hz, 4H), 6.77 (s, 2H), 6.45 (d, J = 7.1 Hz, 1H), 5.23 (s, 2H), 3.54 (d, J = 4.3 Hz, 4H), 2.45 (s, 4H), 2.24 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 142.67, 141.67, 141.53, 141.24, 140.77, 131.55, 130.95, 130.60, 129.71, 128.72, 128.63, 128.59, 127.07, 127.06, 125.90, 123.66, 118.22, 115.83, 105.68, 66.14, 51.52, 49.76, 21.93. HRMS calcd for C 44 H 40 N 3 O + (M – Cl-) 626.3166, found 626.3169. Synthesis of 6-(3,5-Diphenyl-1H-pyrazol-1-yl)picolinaldehyde An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 2-bromo-6-(3,5-diphenyl-1H-pyrazol-1-yl)pyridine (7.52 g, 20 mmol, 1.0 equiv) and dry THF (35 mL). n-BuLi (1.6 M in hexane, 15 mL, 1.2 equiv) was added dropwise at -78 °C and the resulting mixture was stirred at -78 °C for 1 hour. After the indicated time, DMF (1.86 mL, 24 mmol, 1.2 equiv) was added dropwise at -78 °C and the reaction was stirred for 1 hour at -78 °C. After the indicate time, the reaction mixture was diluted with EtOAc (50 mL), washed with H 2 O (1 x 20 mL) and brine (1 x 20 mL). The organic layers were combined, dried, filtered, and concentrated. The residue was purified by chromatography on silica gel to afford the title product (2.6 g, 40%). 1 H NMR (500 MHz, CDCl 3 ) δ 9.54 (s, 1H), 8.05 (d, J = 8.1 Hz, 1H), 7.96 (t, J = 8.0 Hz, 3H), 7.83 (d, J = 7.5 Hz, 1H), 7.48 (t, J = 7.5 Hz, 2H), 7.43 – 7.34 (m, 6H), 6.87 (s, 1H). 13 C NMR (126 MHz, CDCl3) δ 192.57, 153.10, 152.85, 150.91, 145.72, 139.34, 132.49, 131.57, 129.11, 128.76, 128.57, 128.47, 128.07, 126.06, 121.84, 119.15, 107.49. HRMS calcd for C 2 1H15N3NaO + (M + Na + ) 348.1107, found 348.1113. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(3,5-diphenyl-1H-pyrazol-1-yl)im idazo[1,5-a]pyridin- 2-ium chloride (13) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(3,5-diphenyl-1H-pyrazol-1-yl)picolinaldehyde (3.25 g, 10 mmol, 1.0 equiv), 2,6- diisopropylaniline (1.77 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (3.3 g, 62%). 1 H NMR (500 MHz, CDCl 3 ) δ 9.56 (s, 1H), 9.15 (d, J = 9.1 Hz, 1H), 9.03 (s, 1H), 7.92 – 7.78 (m, 2H), 7.60 (t, J = 7.9 Hz, 1H), 7.54 – 7.41 (m, 6H), 7.39 – 7.29 (m, 5H), 7.05 (s, 1H), 6.80 (d, J = 7.1 Hz, 1H), 2.27 (dt, J = 13.5, 6.8 Hz, 2H), 1.30 (d, J = 6.8 Hz, 6H), 1.19 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 155.48, 147.86, 145.06, 133.11, 132.30, 130.90, 130.64, 130.31, 129.66, 129.54, 129.02, 128.86, 128.01, 127.63, 125.93, 124.79, 124.74, 123.01, 122.41, 121.00, 116.10, 106.69, 28.80, 24.67, 24.20. HRMS calcd for C 3 4H33N4 + (M – Cl-) 497.2700, found 497.2699. Synthesis of 5-(9H-Carbazol-9-yl)-2-(2,6-diisopropylphenyl)imidazo[1,5-a] pyridin-2-ium chloride (14) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 6-(9H-carbazol-9-yl)picolinaldehyde (2.72 g, 10 mmol, 1.0 equiv), 2,6-diisopropylaniline (1.77 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH2Cl2/MeOH = 20/1) to afford the title product (3.22 g, 67%). 1 H NMR (500 MHz, CDCl3) δ 9.55 (s, 1H), 9.26 (d, J = 9.3 Hz, 1H), 8.15 (d, J = 7.6 Hz, 2H), 7.82 (s, 1H), 7.73 – 7.64 (m, 1H), 7.58 (d, J = 7.0 Hz, 1H), 7.45 (tt, J = 23.8, 7.6 Hz, 5H), 7.24 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 2.09 (dt, J = 13.5, 6.8 Hz, 2H), 1.23 (d, J = 6.8 Hz, 6H), 0.94 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 144.88, 138.75, 133.30, 132.29, 130.23, 127.54, 127.49, 125.95, 124.66, 124.60, 123.03, 122.87, 121.93, 121.44, 121.15, 119.68, 109.47, 28.76, 24.43, 24.33. HRMS calcd for C 31 H 30 N 3 + (M – Cl-) 444.2434, found 444.2433. S An oven-dried 50 mL round-bottomed flask equipped with a stir bar was charged with 6- methoxypicolinaldehyde (685 mg, 5 mmol, 1.0 equiv), 2,6-diisopropylaniline (885 mg, 5 mmol, 1.0 equiv), paraformaldehyde (225 mg, 7.5 mmol, 1.5 equiv) and EtOH (12 mL). HCl (4.0 M in dioxane, 2.5 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (13 g 75%) 1 H NMR (500 MHz Chloroform-d) δ 9.52 (d, J = 2.0 Hz, 1H), 8.30 (d, J = 1.9 Hz, 1H), 7.88 (d, J = 9.2 Hz, 1H), 7.56 (t, J = 7.8 Hz, 1H), 7.44 (dd, J = 9.2, 7.6 Hz, 1H), 7.32 (d, J = 7.9 Hz, 2H), 6.71 (d, J = 7.5 Hz, 1H), 4.31 (s, 3H), 2.12 (p, J = 6.8 Hz, 2H), 1.16 (dd, J = 12.2, 6.8 Hz, 12H). 13 C NMR (126 MHz, CDCl3) δ 146.72, 145.07, 132.16, 132.14, 130.59, 128.43, 124.63, 122.12, 116.55, 111.19, 93.99, 58.36, 28.68, 24.49, 24.46. HRMS calcd for C 2 0H25N2O + (M – Cl-) 309.1961, found 309.1973. Example 2: Synthesis of Imidazo[1,5-α]pyridine NHC Ligand-Metal Complexes Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene gold(I) chloride (16) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (1) (2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]py ridin-2-ium chloride) (107 mg, 0.3 mmol, 1.0 equiv), AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K 2 CO 3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (150 mg, 90%). 1 H NMR (500 MHz, CDCl3) δ 7.49 (t, J = 7.8 Hz, 1H), 7.31 – 7.22 (m, 3H), 7.17 (d, J = 9.0 Hz, 1H), 6.98 (dd, J = 8.9, 7.2 Hz, 1H), 6.27 (d, J = 6.9 Hz, 1H), 2.94 (s, 6H), 2.21 (dt, J = 13.8, 6.9 Hz, 2H), 1.31 (d, J = 6.8 Hz, 6H), 1.10 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 164.49, 148.63, 145.20, 135.78, 132.55, 130.57, 124.27, 124.12, 113.75, 112.50, 102.48, 44.28, 28.45, 24.50, 24.32. HRMS calcd for C 21 H 27 AuClN 3 Na+ (M + + Na) 576.1451, found 576.1456. Synthesis of 5-(Dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-ylidene gold(I) chloride (17) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (2) (95 mg, 0.3 mmol, 1.0 equiv), AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (111 mg, 72%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.22 (s, 1H), 7.16 (d, J = 9.0 Hz, 1H), 7.01 – 6.92 (m, 3H), 6.26 (d, J = 7.0 Hz, 1H), 2.95 (s, 6H), 2.36 (s, 3H), 2.00 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 163.47, 148.71, 139.62, 136.41, 134.27, 132.87, 129.38, 123.97, 112.62, 112.44, 102.41, 44.32, 21.19, 17.83. HRMS calcd for C 1 8H21AuClN3Na + (M + + Na) 534.0982, found 534.0986. Synthesis of 2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(dimethylamino)imidazo [1,5-a]pyridin-3- ylidene gold(I) chloride (18) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (3) (186 mg, 0.3 mmol, 1.0 equiv), AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (198 mg, 81%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.24 (d, J = 7.6 Hz, 4H), 7.20 – 7.08 (m, 13H), 6.79 (td, J = 7.3, 2.9 Hz, 4H), 6.75 (s, 2H), 6.63 (d, J = 9.0 Hz, 1H), 6.14 (d, J = 6.8 Hz, 1H), 5.86 (s, 1H), 5.32 (s, 2H), 2.82 (s, 6H), 2.24 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 163.95, 148.20, 142.50, 142.16, 141.09, 139.67, 135.99, 131.37, 130.16, 129.61, 129.26, 128.46, 128.32, 126.58, 126.53, 123.30, 115.08, 112.44, 101.94, 51.45, 44.08, 21.88. HRMS calcd for C42H37AuClN3Na + (M + + Na) 838.2234, found 838.2221. Synthesis of 5-(Diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyri din-3-ylidene gold(I) chloride (19) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (4) (116 mg, 0.3 mmol, 1.0 equiv), AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (162 mg, 93%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.49 (t, J = 7.8 Hz, 1H), 7.37 – 7.14 (m, 4H), 6.98 (dd, J = 8.9, 7.1 Hz, 1H), 6.33 (d, J = 6.9 Hz, 1H), 3.32 (dd, J = 14.1, 7.0 Hz, 4H), 2.21 (dt, J = 13.6, 6.7 Hz, 2H), 1.31 (d, J = 6.8 Hz, 6H), 1.20 (t, J = 7.1 Hz, 6H), 1.12 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 164.66, 145.58, 145.18, 135.90, 132.47, 130.49, 124.08, 123.91, 113.78, 113.17, 107.17, 46.44, 28.44, 24.46, 24.35, 11.07. HRMS calcd for C 2 3H31AuClN3Na + (M + + Na) 604.1764, found 604.1770. S D 2 1 I 2 An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (5) (103 mg, 0.3 mmol, 1.0 equiv), AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K 2 CO 3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (110 mg, 68%). 1 H NMR (500 MHz, CDCl3) δ 7.20 (d, J = 8.8 Hz, 2H), 6.99 – 6.90 (m, 3H), 6.34 – 6.27 (m, 1H), 3.31 (q, J = 7.0 Hz, 4H), 2.33 (s, 3H), 1.98 (s, 6H), 1.18 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 163.40, 145.45, 139.47, 136.53, 134.24, 132.83, 129.31, 123.64, 113.37, 112.54, 107.13, 46.48, 21.18, 17.86, 11.08. HRMS calcd for C 2 0H25AuClN3Na + (M + + Na) 562.1295, found 562.1304. Synthesis of 2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(diethylamino)imidazo[ 1,5-a]pyridin-3- ylidene gold(I) chloride (21) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (6) (194 mg, 0.3 mmol, 1.0 equiv), AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (164 mg, 65%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.18 (dd, J = 9.5, 5.4 Hz, 4H), 7.13 – 7.02 (m, 12H), 6.75 – 6.67 (m, 5H), 6.65 (s, 2H), 6.60 (d, J = 9.0 Hz, 1H), 6.12 (d, J = 6.7 Hz, 1H), 5.81 (s, 1H), 5.29 (s, 2H), 3.11 (dd, J = 7.0, 3.6 Hz, 4H), 2.15 (s, 3H), 1.08 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 164.04, 145.21, 142.51, 142.09, 14104 13953 13609 13128 13011 12960 12925 12846 12832 12657 12651 12294 114.95, 113.18, 106.70, 51.53, 46.37, 21.86, 11.16. HRMS calcd for C44H41AuClN3Na + (M + + Na) 866.2547, found 866.2533. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]py ridin-3-ylidene gold(I) chloride (22) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (7) (119 mg, 0.3 mmol, 1.0 equiv), AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (200 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (151 mg, 85%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.49 (t, J = 7.8 Hz, 1H), 7.25 (d, J = 5.8 Hz, 3H), 7.17 (d, J = 9.0 Hz, 1H), 6.97 (dd, J = 9.0, 7.1 Hz, 1H), 6.30 (d, J = 7.0 Hz, 1H), 3.55 – 3.39 (m, 2H), 2.65 (t, J = 10.8 Hz, 2H), 2.42 (td, J = 12.8, 3.7 Hz, 2H), 2.20 (dq, J = 13.7, 6.8 Hz, 2H), 1.96 (d, J = 13.0 Hz, 1H), 1.70 (d, J = 13.3 Hz, 2H), 1.31 (d, J = 6.8 Hz, 7H), 1.10 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 164.34, 148.90, 145.18, 135.86, 132.46, 130.54, 124.32, 124.11, 113.76, 112.84, 103.06, 53.62, 28.46, 25.26, 24.51, 24.30, 24.20. HRMS calcd for C 2 4H31AuClN3Na + (M + + Na) 616.1764, found 616.1760. S An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (8) (107 mg, 0.3 mmol, 1.0 equiv), AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K 2 CO 3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (200 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (104 mg, 63%). 1 H NMR (500 MHz, CDCl3) δ 7.22 (s, 1H), 7.18 (d, J = 8.8 Hz, 1H), 7.01 – 6.92 (m, 3H), 6.30 (d, J = 6.6 Hz, 1H), 3.49 (d, J = 10.9 Hz, 2H), 2.72 – 2.61 (m, 2H), 2.44 (ddt, J = 16.1, 12.6, 6.4 Hz, 2H), 2.34 (s, 3H), 1.98 (d, J = 15.0 Hz, 7H), 1.72 (d, J = 13.3 Hz, 2H), 1.44 – 1.31 (m, 1H). 13 C NMR (126 MHz, CDCl3) δ 163.10, 148.92, 139.54, 136.51, 134.26, 132.82, 129.34, 124.02, 113.07, 112.52, 103.17, 53.69, 25.32, 24.20, 21.18, 17.87. HRMS calcd for C 21 H 25 AuClN 3 Na + (M + + Na) 574.1295, found 574.1297. Synthesis of 2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(piperidin-1-yl)imidaz o[1,5-a]pyridin-3- ylidene gold(I) chloride (24) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (9) (198 mg, 0.3 mmol, 1.0 equiv), AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K 2 CO 3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (200 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (154 mg, 60%). 1 H NMR (500 MHz, CDCl3) δ 7.24 (d, J = 7.6 Hz, 4H), 7.16 (ddd, J = 21.6, 15.7, 7.3 Hz, 12H), 6.83 – 6.76 (m, 5H), 6.75 (s, 2H), 6.68 (d, J = 9.0 Hz, 1H), 6.15 (d, J = 6.9 Hz, 1H), 5.98 (s, 1H), 5.29 (s, 2H), 3.23 (d, J = 10.7 Hz, 2H), 250 (t J = 108 Hz 2H) 230 (dd J = 257 128 Hz 2H) 221 (d J = 151 Hz 3H) 195 (d J = 13.0 Hz, 1H), 1.62 (d, J = 13.1 Hz, 2H), 1.37 – 1.26 (m, 1H). 13 C NMR (126 MHz, CDCl3) δ 163.96, 148.42, 142.68, 142.01, 141.05, 139.62, 136.07, 131.42, 130.15, 129.63, 129.35, 128.45, 128.32, 126.53, 126.51, 123.48, 114.83, 112.77, 102.49, 53.32, 51.40, 25.36, 24.19, 21.87. HRMS calcd for C45H41AuClN3Na + (M + + Na) 878.2547, found 878.2536. Synthesis of 2-(2,6-Diisopropylphenyl)-5-methoxyimidazo[1,5-a]pyridin-3-y lidene gold(I) chloride (25) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (10) (103 mg, 0.3 mmol, 1.0 equiv), AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by chromatography on silica gel to afford the title product as a white solid (57 mg, 35%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.52 (t, J = 7.7 Hz, 1H), 7.30 (dd, J = 7.9, 2.1 Hz, 2H), 7.14 – 7.09 (m, 1H), 7.05 (t, J = 7.9 Hz, 1H), 5.98 (d, J = 7.1 Hz, 1H), 4.15 (d, J = 2.1 Hz, 3H), 2.24 (p, J = 6.9 Hz, 2H), 1.32 (dd, J = 6.9, 2.0 Hz, 6H), 1.12 (dd, J = 7.0, 2.2 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 162.07, 150.39, 145.23, 135.47, 132.13, 130.64, 124.83, 124.16, 113.12, 109.51, 89.06, 56.68, 28.39, 24.53, 24.37. HRMS calcd for C 2 0H24AuClN2ONa + (M + + Na) 563.1135, found 563.1170. Synthesis of cinnamyl[2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[ 1,5-a]pyridine-3- ylidene]chloropalladium(II) (26) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (1) (157 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl} 2 ] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH 2 Cl 2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (181 mg, 78%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.59 (t, J = 7.8 Hz, 1H), 7.43 – 7.28 (m, 10H), 7.21 – 7.15 (m, 1H), 5.90 (dd, J = 22.6, 9.0 Hz, 1H), 4.99 (d, J = 13.3 Hz, 1H), 3.03 (s, 6H), 2.54 (d, J = 9.3 Hz, 2H), 2.29 (dd, J = 13.3, 6.6 Hz, 2H), 1.22 (d, J = 6.8 Hz, 6H), 1.15 (d, J = 6.8 Hz, 6H). 13 C NMR (151 MHz, CDCl3) δ 165.54, 148.39, 145.29, 136.84, 135.50, 131.31, 130.76, 129.28, 127.56, 126.32, 126.08, 124.01, 118.74, 115.87, 114.00, 100.73, 77.00, 49.98, 38.16, 28.39, 24.90, 23.67. HRMS calcd for C 3 0H36N3Pd + (M – Cl-) 544.1939, found 544.1937. Synthesis of cinnamyl[5-(Dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II) (27) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (2) (139 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl} 2 ] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH2Cl2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (97 mg, 45%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.21 (ddd, J = 21.9, 14.8, 7.6 Hz, 5H), 7.14 – 7.09 (m, 2H), 7.00 (s, 2H), 6.94 (dd, J = 9.0, 7.1 Hz, 1H), 6.75 (d, J = 6.9 Hz, 1H), 5.95 (dt, J = 14.1, 9.0 Hz, 1H), 5.29 (d, J = 14.1 Hz, 1H), 2.97 (s, 6H), 2.58 (d, J = 9.0 Hz, 2H), 2.33 (s, 3H), 2.00 (s, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 163.87, 149.00, 139.89, 138.53, 135.86, 134.77, 134.15, 131.85, 129.24, 128.87, 128.70, 128.25, 127.97, 126.47, 126.03, 124.76, 115.71, 112.89, 105.09, 49.22, 21.24, 17.89. HRMS calcd for C 2 7H30N3Pd + (M – Cl-) 502.1469, found 502.1468. Synthesis of cinnamyl[2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(dimethylamin o)imidazo[1,5- a]pyridin-3-ylidene]chloropalladium(II) (28) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (3) (273 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl}2] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH 2 Cl 2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (253 mg, 75%). 1 H NMR (500 MHz, CDCl3) δ 7.59 (d, J = 7.0 Hz, 1H), 7.30 – 7.25 (m, 3H), 7.19 (dd, J = 7.0, 4.0 Hz, 8H), 7.15 – 7.09 (m, 6H), 7.05 (dd, J = 9.1, 7.1 Hz, 1H), 6.95 – 6.88 (m, 7H), 6.78 – 6.71 (m, 4H), 6.28 (s, 1H), 5.37 (dt, J = 13.1, 9.2 Hz, 1H), 4.98 (s, 2H), 4.50 (d, J = 13.3 Hz, 1H), 2.89 (s, 6H), 2.28 (s, 3H), 2.22 (d, J = 9.1 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 166.53, 148.06, 142.66, 141.29, 141.05, 140.06, 136.11, 135.42, 129.81, 129.63, 129.58, 128.76, 128.66, 128.53, 128.24, 126.90, 126.80, 126.59, 126.11, 115.83, 114.87, 114.33, 107.81, 95.36, 77.10, 51.87, 50.45, 43.18, 21.97. HRMS calcd for C51H46N3Pd + (M – Cl-) 806.2721, found 806.2713. Synthesis of cinnamyl[5-(Diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1 ,5-a]pyridin-3- ylidene]chloropalladium(II) (29) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (4) (170 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl} 2 ] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH2Cl2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (148 mg, 61%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.49 (t, J = 7.8 Hz, 1H), 7.31 – 7.22 (m, 3H), 7.17 (d, J = 9.0 Hz, 1H), 6.98 (dd, J = 8.9, 7.2 Hz, 1H), 6.27 (d, J = 6.9 Hz, 1H), 2.94 (s, 6H), 2.21 (dt, J = 13.8, 6.9 Hz, 2H), 1.31 (d, J = 6.8 Hz, 6H), 1.10 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 167.18, 145.13, 144.53, 141.70, 135.83, 135.70, 134.79, 131.50, 130.98, 129.77, 128.69, 127.20, 126.16, 124.08, 122.82, 116.21, 113.18, 109.23, 72.21, 66.27, 57.74, 28.51, 24.34, 23.88, 13.32. HRMS calcd for C 3 2H40N3Pd + (M – Cl-) 572.2252, found 572.2248. Synthesis of cinnamyl[5-(Diethylamino)-2-mesitylimidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II) (30) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (5) (151 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl} 2 ] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH2Cl2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (79 mg, 35%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.49 (t, J = 7.8 Hz, 1H), 7.31 – 7.22 (m, 3H), 7.17 (d, J = 9.0 Hz, 1H), 6.98 (dd, J = 8.9, 7.2 Hz, 1H), 6.27 (d, J = 6.9 Hz, 1H), 2.94 (s, 6H), 2.21 (dt, J = 13.8, 6.9 Hz, 2H), 1.31 (d, J = 6.8 Hz, 6H), 1.10 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 164.61, 144.79, 140.13, 137.33, 135.77, 134.42, 131.56, 129.34, 129.26, 127.49, 125.86, 125.71, 116.38, 112.39, 107.38, 57.15, 21.25, 17.59, 13.17. HRMS calcd for C 2 9H34N3Pd + (M – Cl-) 530.1782, found 530.1779. Synthesis of cinnamyl[2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(diethylamino )imidazo[1,5- a]pyridin-3-ylidene]chloropalladium(II) (31) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (6) (285 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl}2] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH2Cl2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (237 mg, 68%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.94 (d, J = 7.0 Hz, 1H), 7.29 (dd, J = 4.9, 1.4 Hz, 2H), 7.21 (dd, J = 5.0, 2.9 Hz, 5H), 7.16 (dd, J = 7.9, 3.4 Hz, 4H), 7.11 (dd, J = 5.8, 3.6 Hz, 6H), 6.97 (t, J = 8.4 Hz, 2H), 6.94 – 6.87 (m, 6H), 6.72 – 6.64 (m, 4H), 6.27 (s, 1H), 5.36 – 5.28 (m, 1H), 4.92 (s, 2H), 4.40 (d, J = 12.9 Hz, 1H), 3.61 (s, 2H), 2.59 (s, 2H), 2.29 (s, 5H), 1.00 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 166.64, 144.35, 142.68, 141.09, 140.70, 140.14, 135.80, 135.14, 130.80, 129.99, 129.74, 129.35, 128.81, 128.62, 128.60, 127.03, 126.93, 126.80, 126.14, 115.88, 114.08, 112.52, 109.30, 90.41, 57.71, 51.80, 47.36, 21.98, 13.84. HRMS calcd for C 53 H 50 N 3 Pd + (M – Cl-) 834.3034, found 834.3020. Synthesis of cinnamyl[2-(2,6-Diisopropylphenyl)-5-(piperidin-1-yl)imidazo [1,5-a]pyridin-3- ylidene]chloropalladium(II) (32) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (7) (175 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl} 2 ] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH 2 Cl 2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (176 mg, 71%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.42 (t, J = 7.8 Hz, 1H), 7.25 (dd, J = 17.4, 7.5 Hz, 4H), 7.21 – 7.08 (m, 4H), 7.02 (d, J = 9.0 Hz, 1H), 6.77 (dd, J = 9.0, 7.1 Hz, 1H), 6.23 (d, J = 6.9 Hz, 1H), 5.26 (dt, J = 12.7, 9.2 Hz, 1H), 4.57 – 4.48 (m, 1H), 3.34 (s, 2H), 2.50 (dd, J = 21.4, 14.7 Hz, 4H), 2.30 (d, J = 7.6 Hz, 2H), 1.69 (s, 6H), 1.21 (d, J = 6.8 Hz, 6H), 0.99 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 171.48, 149.74, 146.03, 138.10, 137.15, 133.36, 130.02, 128.39, 127.01, 126.63, 124.19, 123.46, 114.90, 113.41, 107.73, 103.38, 88.43, 77.10, 53.74, 44.45, 28.18, 26.14, 25.87, 23.85, 23.02. HRMS calcd for C 3 3H40N3Pd + (M – Cl-) 584.2252, found 584.2247. Synthesis of cinnamyl[2-Mesityl-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3 - ylidene]chloropalladium(II) (33) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (8) (157 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl} 2 ] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH 2 Cl 2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (120 mg, 52%). 1 H NMR (500 MHz, CDCl3) δ 7.24 (d, J = 7.4 Hz, 2H), 7.16 (dd, J = 16.2, 6.6 Hz, 3H), 7.10 (t, J = 7.2 Hz, 1H), 7.00 (d, J = 9.0 Hz, 1H), 6.93 (s, 2H), 6.73 (dd, J = 8.9, 7.0 Hz, 1H), 6.14 (d, J = 6.9 Hz, 1H), 5.27 (dt, J = 12.3, 9.3 Hz, 1H), 4.48 (d, J = 12.5 Hz, 1H), 3.41 (s, 2H), 2.54 (s, 4H), 2.31 (s, 3H), 2.02 (s, 6H), 1.89-1.59 (m, 6H). 13 C NMR (126 MHz, CDCl3) δ 170.76, 150.22, 138.98, 138.58, 137.57, 135.46, 134.34, 128.72, 128.46, 127.12, 126.62, 123.55, 113.52, 113.22, 108.13, 102.98, 86.94, 53.95, 45.70, 26.25, 24.10, 21.21, 18.32. HRMS calcd for C 3 0H34N3Pd + (M – Cl-) 542.1782, found 542.1788. Synthesis of cinnamyl[2-(2,6-Dibenzhydryl-4-methylphenyl)-5-(piperidin-1- yl)imidazo[1,5- a]pyridin-3-ylidene]chloropalladium(II) (34) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (9) (290 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl}2] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH 2 Cl 2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (265 mg, 75%). 1 H NMR (500 MHz, CDCl3) δ 7.41 (d, J = 7.6 Hz, 2H), 7.26 (t, J = 7.5 Hz, 2H), 7.22 – 7.06 (m, 13H), 7.01 (dd, J = 10.2, 5.3 Hz, 7H), 6.79 (s, 2H), 6.75 – 6.69 (m, 4H), 6.55 (dd, J = 8.9, 7.0 Hz, 1H), 6.36 (d, J = 9.0 Hz, 1H), 6.10 (d, J = 6.8 Hz, 1H), 5.54 (s, 2H), 5.43 (s, 1H), 5.22 (dt, J = 12.6, 9.1 Hz, 1H), 4.72 (d, J = 12.8 Hz, 1H), 3.49 (s, 2H), 2.58 (s, 2H), 2.20 (s, 3H), 2.11 (d, J = 8.7 Hz, 2H), 1.81 (d, J = 85.5 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 170.59, 149.54, 144.17, 142.35, 142.06, 138.71, 138.23, 137.12, 132.11, 130.15, 129.17, 129.13, 128.57, 128.34, 128.10, 127.35, 126.87, 126.41, 126.18, 123.11, 116.46, 113.35, 107.52, 102.58, 88.51, 53.32, 51.24, 45.07, 26.14, 24.12, 21.97. HRMS calcd for C54H50N3Pd + (M – Cl-) 846.3034, found 846.3021. Synthesis of cinnamyl[2-(2,6-Diisopropylphenyl)-5-morpholinoimidazo[1,5-a ]pyridin-3- ylidene]chloropalladium(II) (35) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (10) (176 mg, 0.44 mmol, 2.2 equiv), [{Pd(cin)Cl}2] (103 mg, 0.20 mmol, 1.0 equiv) and KOtBu (54 mg, 0.48 mmol, 2.4 equiv), placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (8 mL) was added and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with CH 2 Cl 2 and filtered. The solution was collected and concentrated. The title product was obtained by trituration from diethyl ether/hexanes (1:10 v/vol) as a yellow solid (104 mg, 42%). 1 H NMR (500 MHz, CDCl3) δ 7.42 (d, J = 7.7 Hz, 1H), 7.31 – 7.10 (m, 8H), 7.04 (d, J = 9.0 Hz, 1H), 6.81 – 6.72 (m, 1H), 6.17 (d, J = 6.8 Hz, 1H), 5.21 (dd, J = 21.1, 9.2 Hz, 1H), 4.51 (d J = 127 Hz 1H) 387 (d J = 49 Hz 4H) 324 (s 2H) 286 (s 2H) 252 (s 2H) 228 (s 2H), 1.23 (d, J = 6.7 Hz, 5H), 0.99 (d, J = 6.7 Hz, 5H). 13 C NMR (126 MHz, CDCl3) δ 172.36, 148.60, 146.20, 137.98, 137.30, 133.58, 130.14, 129.04, 128.53, 127.95, 127.11, 126.85, 123.85, 123.55, 115.42, 113.90, 107.08, 103.30, 87.70, 67.29, 51.99, 45.08, 28.30, 26.42, 22.97. HRMS calcd for C 3 2H38N3OPd + (M – Cl-) 586.2044, found 586.2046. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene silver(I) chloride (36) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (1) (107 mg, 0.3 mmol, 1.0 equiv) and Ag 2 O (83.4 mg, 0.36 mmol, 1.2 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. CH2Cl2(6.0 ml, 0.05 M) was added and the reaction mixture was stirred at room temperature for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (125.5 mg, 90%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.49 (t, J = 7.8 Hz, 1H), 7.33 (s, 1H), 7.28 (d, J = 7.8 Hz, 2H), 7.22 (d, J = 9.1 Hz, 1H), 7.00 (t, J = 8.0 Hz, 1H), 6.32 (d, J = 7.0 Hz, 1H), 2.93 (s, 6H), 2.25 – 2.13 (m, 2H), 1.24 (d, J = 6.8 Hz, 6H), 1.11 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 172.86 (dd, J = 262.3, 18.9 Hz), 148.66, 145.25, 136.02, 132.87 (d, J = 6.5 Hz), 130.51, 124.24, 124.12, 114.39 (d, J = 6.5 Hz), 112.80, 102.08, 43.89, 28.26, 24.66, 24.42. HRMS calcd for C 2 1H27AgClN3Na + (M + + Na) 486.0837, found 486.0849. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene copper(I) chloride (37) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (1) (107 mg, 0.3 mmol, 1.0 equiv), CuCl (29.7 mg, 0.3 mmol, 1.0 equiv) and NaOtBu (28.8 mg, 0.3 mmol, 1.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at room temperature for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a brown solid (107.2 mg, 85%). 1 H NMR (500 MHz, CDCl3) δ 7.39 (t, J = 7.7 Hz, 1H), 7.18 (t, J = 9.5 Hz, 3H), 7.13 (d, J = 9.1 Hz, 1H), 6.93 – 6.86 (m, 1H), 6.25 (d, J = 6.7 Hz, 1H), 2.88 (s, 6H), 2.15 (dt, J = 13.3, 6.5 Hz, 2H), 1.18 (d, J = 6.7 Hz, 6H), 1.04 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 169.43, 148.75, 145.22, 135.84, 132.15, 130.28, 124.26, 124.09, 123.96, 122.95, 113.86, 112.91, 101.93, 43.72, 28.30, 24.75, 24.24. HRMS calcd for C 21 H 27 ClCuN 3 Na + (M + + Na) 442.1082, found 442.1094. Synthesis of 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idine-3(2H)-selenone (A1) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (1) (107 mg, 0.3 mmol, 1.0 equiv), selenium powder (47.4 mg, 0.6 mmol, 2.0 equiv) and KOtBu (83 mg, 0.45 mmol, 1.5 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at room temperature for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The residue was purified by chromatography on silica gel to afford the title product (110.5 g, 92%). 1 H NMR (500 MHz, CDCl3) δ 7.48 (t, J = 7.7 Hz, 1H), 7.38 – 7.24 (m, 2H), 7.09 (s, 1H), 6.88 (d, J = 9.0 Hz, 1H), 6.70 (dd, J = 8.8, 7.1 Hz, 1H), 5.93 (d, J = 6.8 Hz, 1H), 2.84 (s, 6H), 2.31 (dt, J = 13.6, 6.8 Hz, 2H), 1.30 (d, J = 6.8 Hz, 6H), 1.08 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 149.66, 148.15, 145.80, 134.90, 132.80, 130.06, 124.20, 123.53, 123.47, 111.91, 111.15, 98.97, 45.32, 28.79, 24.70, 23.24. 77 Se NMR (95 MHz, CDCl3) δ 214.65. HRMS calcd for C 2 1H27N3NaSe + (M + + Na) 424.1262, found 424.1273. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3- ylidene(cyclooctadiene)rhodium(I) chloride (38) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (1) (107 mg, 0.3 mmol, 1.0 equiv), [Rh(cod)Cl] 2 (74 mg, 0.15 mmol, 0.5 equiv) and KOtBu (47.1 mg, 0.42 mmol, 1.4 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. THF (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at room temperature for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (129.5 mg, 76%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.52 (t, J = 7.8 Hz, 1H), 7.32 (d, J = 7.8 Hz, 2H), 7.12 (d, J = 12.1 Hz, 2H), 6.91 (dd, J = 9.0, 7.0 Hz, 1H), 6.69 (d, J = 6.9 Hz, 1H), 4.67 (s, 2H), 3.26 (s, 2H), 3.20 (s, 6H), 2.59 (dt, J = 13.5, 6.7 Hz, 2H), 2.20 (s, 2H), 1.98 (s, 2H), 1.70 (s, 2H), 1.58 (d, J = 7.0 Hz, 2H), 1.34 (d, J = 6.8 Hz, 6H), 1.08 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 168.99 (d, J = 51.0 Hz), 150.31, 145.97, 135.70, 132.18, 130.29, 128.66, 124.62, 123.83, 115.47, 114.62, 103.79, 94.78, 65.69 (d, J = 18.4 Hz), 47.69, 32.71, 28.38, 28.27, 25.98, 23.14. HRMS calcd for C 2 9H39N3Rh + (M – Cl-) 532.2194, found 532.2189. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3- ylidene(cyclooctadiene)rhodium(I) triflate (39) An oven-dried flask equipped with a stir bar was charged with the corresponding [Rh(NHC)(cod)]Cl complex (38) (113.6 mg, 0.2 mmol, 1.0 equiv), AgOTf (51.4 mg, 0.2 mmol, 1.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. CH 2 Cl 2 (2.0 ml, 0.1 M) was added and the reaction mixture was stirred at room temperature for 1 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained as a yellow solid (109 mg, 80%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.53 (t, J = 7.8 Hz, 1H), 7.40 (dd, J = 6.1, 3.7 Hz, 1H), 7.30 (s, 1H), 7.28 (s, 1H), 7.21 (s, 1H), 7.20 – 7.17 (m, 2H), 4.61 (s, 2H), 3.73 (d, J = 2.9 Hz, 2H), 3.26 (s, 6H), 2.30 (ddd, J = 20.4, 13.8, 6.2 Hz, 4H), 2.17 – 2.08 (m, 2H), 1.93 (dd, J = 13.9, 5.9 Hz, 2H), 1.79 (dd, J = 14.1, 6.9 Hz, 2H), 1.37 (d, J = 6.8 Hz, 6H), 1.11 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 161.16, 160.72, 148.48, 144.93, 133.67, 131.34, 130.88, 126.18, 124.29, 116.56, 115.26, 105.09, 98.55, 98.49, 73.00, 72.89, 49.83, 31.44, 28.51, 28.47, 26.07, 22.60. 19 F NMR (471 MHz, CDCl 3 ) δ -78.00. HRMS calcd for C 29 H 39 N 3 Rh + (M – OTf -) 532.2194, found 532.2202. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3- ylidene(bis(carbonyl))rhodium(I) triflate (40) An oven-dried flask equipped with a stir bar was charged with the corresponding [Rh(NHC)(cod)]OTf complex (39) (68.2 mg, 0.1 mmol, 1.0 equiv) and 5 ml THF. CO gas was bubbled through the reaction and the reaction mixture was stirred at room temperature for 2 hours. The resulting mixture was concentrated and the title product was obtained as a yellow solid (566 mg 90%) 1 H NMR (500 MHz CDCl ) δ 767 754 (m 4H) 736 (d J = 75 Hz 3H), 3.71 – 3.56 (m, 6H), 2.23 – 2.14 (m, 2H), 1.29 (d, J = 6.6 Hz, 6H), 1.18 (d, J = 6.6 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 185.12 (d, J = 57.7 Hz), 182.70 (d, J = 73.5 Hz), 163.97 (d, J = 48.4 Hz), 146.42, 145.44, 134.00, 131.90, 131.74, 127.17, 124.51, 117.77, 115.47, 108.25, 54.05, 28.47, 24.71, 24.13. 19 F NMR (471 MHz, CDCl3) δ -78.23. HRMS calcd for C 2 3H27N3O2Rh + (M – OTf -) 480.1153, found 480.1177. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene An oven-dried flask equipped with a stir bar was charged with the corresponding Au(NHC)Cl complex (16) (55.5 mg, 0.1 mmol, 1.0 equiv) and AgNTf 2 (38.8 mg, 0.1 mmol, 1.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. CH2Cl2 (1.0 mL, 0.1 M) was added and the reaction mixture was stirred at room temperature for 0.5 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (5 mL), filtered and concentrated. The title product was obtained as a brown solid (68 mg, 85%). 1 H NMR (500 MHz, CDCl3) δ 7.54 (t, J = 7.8 Hz, 1H), 7.37 (s, 1H), 7.30 (d, J = 7.8 Hz, 2H), 7.25 – 7.21 (m, 1H), 7.05 (dd, J = 9.1, 7.1 Hz, 1H), 6.37 (dd, J = 7.0, 0.7 Hz, 1H), 2.90 (s, 6H), 2.16 (dt, J = 13.7, 6.9 Hz, 2H), 1.29 (d, J = 6.9 Hz, 6H), 1.12 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 156.42, 148.35, 145.07, 135.44, 132.84, 130.70, 124.72, 124.12, 119.15 (dd, J = 646.9, 323.4 Hz), 114.47, 112.80, 103.20, 43.75, 28.51, 24.86, 23.55. 19 F NMR (471 MHz, CDCl 3 ) δ -75.25. HRMS calcd for C 23 H 30 AuN 4 + (M – NTf 2 - + CH3CN) 559.2131, found 559.2147. Synthesis of 2-(2,6-diisopropylphenyl)-5-(morpholin-4-yl)imidazo[1,5-a]py ridin-3-ylidene gold(I) chloride (42) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (10) (120 mg, 0.3 mmol, 1.0 equiv), Ag 2 O (83.4 mg, 0.36 mmol, 1.2 equiv), NaCl (35 mg, 0.6 mmol, 2.0 equiv), KCl (45 mg, 0.6 mmol, 2.0 equiv) and 4Å MS (240 mg). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Anhydrous THF (4.0 mL) was added and the reaction mixture was stirred at 90 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was directly used for next step without further purification. The above residue silver complex was dissolved in DCM (4 mL), AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) was added. The mixture was stirred at room temperature for 6 hours. The solution was filtered and concentrated. The residue was purified by chromatography on silica gel to afford the title product (107 mg, 60%). 1 H NMR (500 MHz, Chloroform-d) δ 7.51 (t, J = 7.8 Hz, 1H), 7.29 (d, J = 4.2 Hz, 2H), 7.27 (s, 1H), 7.24 (dd, J = 9.0, 1.0 Hz, 1H), 7.01 (dd, J = 9.1, 7.0 Hz, 1H), 6.38 (dd, J = 7.1, 1.1 Hz, 1H), 4.47 (td, J = 11.6, 2.3 Hz, 2H), 3.91 (dd, J = 11.9, 3.0 Hz, 2H), 3.43 – 3.37 (m, 2H), 3.00 (td, J = 11.5, 3.1 Hz, 2H), 2.20 (p, J = 6.8 Hz, 2H), 1.31 (d, J = 6.8 Hz, 6H), 1.11 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 164.06, 147.35, 145.12, 135.69, 132.41, 130.69, 124.18, 124.12, 114.19, 113.80, 103.75, 66.22, 52.29, 28.48, 24.53, 24.29. HRMS calcd for C 2 3H29AuN3O + (M – Cl-) 560.1971, found 560.1950. Synthesis of 2-(2,4,6-trimethylphenyl)-5-(morpholin-4-yl)imidazo[1,5-a]py ridin-3-ylidene gold(I) chloride (43) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (11) (107 mg, 0.3 mmol, 1.0 equiv), Ag2O (83.4 mg, 0.36 mmol, 1.2 equiv), NaCl (35 mg, 0.6 mmol, 2.0 equiv), KCl (45 mg, 0.6 mmol, 2.0 equiv) and 4Å MS (240 mg). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Anhydrous THF (4.0 mL) was added and the reaction mixture was stirred at 90 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was directly used for next step without further purification. The above residue silver complex was dissolved in DCM (4 mL), AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) was added. The mixture was stirred at room temperature for 6 hours. The solution was filtered and concentrated. The residue was purified by chromatography on silica gel to afford the title product (91 mg, 65%). 1 H NMR (500 MHz, Chloroform-d) δ 7.28 (d, J = 2.3 Hz, 1H), 7.25 (dd, J = 9.2, 1.0 Hz, 1H), 7.03 – 6.95 (m, 3H), 6.37 (dd, J = 7.0, 1.0 Hz, 1H), 4.47 (td, J = 11.6, 2.2 Hz, 2H), 3.94 – 3.85 (m, 2H), 3.45 – 3.34 (m, 2H), 2.99 (td, J = 11.5, 3.1 Hz, 2H), 2.34 (s, 3H), 1.98 (s, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 162.77, 147.26, 139.68, 136.34, 134.18, 132.78, 129.39, 123.87, 114.03, 112.99, 103.80, 66.23, 52.28, 21.19, 17.84. HRMS calcd for C 2 1H23AuClN3O + (M + H + ) 554.1268, found 554.1291 Example 3: Representative Decagram-Scale Synthesis of NHC (e.g., 2-(2,6- Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyridin-2- ium chloride) (1) An oven-dried 500 mL round-bottomed flask equipped with a stir bar was charged with 2,6-dibromopyridine (23.69 g, 100 mmol, 1.0 equiv), dimethylamine solution (63.3 ml, 500 mmol, 5.0 equiv, 40 wt% in H 2 O), K 2 CO 3 (15.2 g, 110 mmol, 1.1 equiv) and CH 3 CN (100 mL). The mixture was refluxed at 100 °C until the starting material was fully consumed (48-72 hours). Then, the mixture was cooled down to room temperature and extracted with EtOAc (100 mL x 2). The organic layers were combined, dried over Na2SO4, filtered, and concentrated to afford 6- bromo-N,N-dimethylpyridin-2-amine (19.7 g, 98%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.23 (t, J = 7.9 Hz, 1H), 6.65 (d, J = 7.4 Hz, 1H), 6.37 (d, J = 8.4 Hz, 1H), 3.08 – 3.03 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 159.21, 140.13, 139.11, 114.19, 103.87, 37.92. An oven-dried 500 mL round-bottomed flask equipped with a stir bar was charged with 6-bromo-N,N-dimethylpyridin-2-amine (19.7 g, 98 mmol, 1.0 equiv) and dry THF (200 mL). n- BuLi (2.5 M in hexane, 59 mL, 1.5 equiv) was slowly added at -78 °C under argon and the resulting mixture was stirred at -78 °C for 1 hour. After the indicated time, anhydrous DMF (9.1 mL, 117.6 mmol, 1.2 equiv) was added dropwise at -78 °C and the reaction was stirred for 1 hour at -78 °C under argon. After the indicated time, the reaction mixture was quenched with NaHCO3 (50 mL, sat., aq.), diluted with EtOAc (300 mL), washed with H2O (100 mL x 2) and brine (50 mL). The organic layers were collected, dried over Na2SO4, filtered, and concentrated. The resulting brown oil was used directly in the next step (75% yield, 1 H NMR). Step 3. Synthesis of (E)-6-(((2,6-Diisopropylphenyl)imino)methyl)-N,N-dimethylpyr idin-2-amine (S3) An oven-dried 500 mL round-bottomed flask equipped with a stir bar was charged with crude 6-(dimethylamino)picolinaldehyde (73.5 mmol based on 1 H NMR yield), 2,6- diisopropylaniline (13.03 g, 73.5 mmol, 1.0 equiv) and dry EtOH (150 mL) and the reaction mixture was stirred at 90 °C for 24 hours. After the indicated time, the reaction mixture was concentrated, cooled down to room temperature and settled overnight to form crystals. The resulting crystals were filtered and recrystallized from CH2Cl2/hexane 3 times to afford analytically pure imine as a yellow solid (17.29 g, 76%). 1 H NMR (500 MHz, CDCl3) δ 8.28 (s, 1H), 7.76 – 7.59 (m, 2H), 7.35 – 7.15 (m, 3H), 6.69 (d, J = 8.0 Hz, 1H), 3.21 (s, 6H), 3.12 (dt, J = 13.7, 6.8 Hz, 2H), 1.29 (d, J = 6.9 Hz, 12H). 13 C NMR (126 MHz, CDCl 3 ) δ 144.91, 144.05, 132.33, 131.98, 130.74, 127.34, 124.49, 123.67, 117.23, 113.60, 105.27, 41.91, 28.68, 24.54, 24.20. HRMS calcd for C 2 0H28N3 + (M + H + ) 310.2278, found 310.2293. Step 4. Synthesis of 2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-2-ium chloride (1) An oven-dried 250 mL round-bottomed flask equipped with a stir bar was charged with (E)-6-(((2,6-Diisopropylphenyl)imino)methyl)-N,N-dimethylpyr idin-2-amine (11.76 g, 38 mmol, 1.0 equiv), paraformaldehyde (1.71 g, 57 mmol, 1.5 equiv) and EtOH (70 mL). HCl (4.0 M in dioxane, 19 mL, 2.0 equiv) was added slowly at 0 °C, the reaction was warmed up to room temperature and stirred at 70 °C for 36 hours. After the indicated time, the reaction was cooled down to room temperature, neutralized with NaHCO 3 , filtered and concentrated. The residue was dissolved in 100 mL CH2Cl2 and mixed with 100 g of silica gel. Then, CH2Cl2 was evaporated and the resulting solid material washed with CH 2 Cl 2 (300 mL) and filtered using filtration funnel. The CH 2 Cl 2 washing and filtration procedure was repeated 4 times. The organic layers were discarded. The solid material was washed with CH2Cl2/MeOH (20/1, 200 mL) and filtered. The CH2Cl2/MeOH washing and filtration procedure was repeated 4 times. The CH2Cl2/MeOH organic layers were combined and concentrated. The resulting solid was dried in an oven at 175 °F for 16 hours. The final product was obtained as a yellow solid (10.88 g, 80%, purity > 98%). Example 4: Synthesis of Imidazo[1,5-a]quinoline N-Heterocyclic Carbene (NHC) Ligands General Procedure Step 1 - Synthesis of N,N-disubstituted-2-nitroaniline (4-2) An oven-dried 500 mL round-bottomed flask equipped with a stir bar was charged with (4-1) (28.2 g, 200 mmol, 1.0 equiv), K 2 CO 3 (33.2 g, 240 mmol, 1.2 equiv), amine (HNR b1 R b2 ) (300 mmol, 1.5 equiv) and acetonitrile (200 mL) at room temperature. The mixture was refluxed for 24 hours. After the indicated time, the reaction mixture was cooled down to room temperature, filtered, and concentrated. The residue was dissolved in 200 mL CH 2 Cl 2 , washed with H2O (2 x 100 mL) and brine (1 x 50 mL). The organic layers were combined, dried over Na2SO4, filtered, and concentrated. The residue was directly used for the next step without further purification. Step 2 – Synthesis of N 1 ,N 1 -disubstituted benzene-1,2-diamine (4-3) An oven-dried 1000 mL round-bottomed flask equipped with a stir bar was charged with (4-2), iron powder (58.85 g, 1000 mmol, 5.0 equiv), acetic acid (400 mmol, 2.0 equiv) and EtOH/H2O (500 mL/50 mL). The mixture was refluxed for 24 hours. After the indicated time, the reaction was cooled down to room temperature, filtered and concentrated. The residue was dissolved in 400 mL ethyl acetate and washed with H 2 O (2 x 200 mL) and brine (1 x 50 mL). The organic layers were combined, dried over Na2SO4, filtered, and concentrated. The residue was directly used for the next step without further purification. Step 3 – Synthesis of N,N-disubstituted-2-methylquinolin-8-amine (4-4) An oven-dried 500 mL round-bottomed flask equipped with a stir bar was charged with (4-3).6 N HCl (250 mL) was added slowly at 0 °C, then, crotonaldehyde (33.1 mL, 400 mmol, 2.0 equiv) was slowly added at 0 °C, followed by addition of toluene (150 mL). The mixture was stirred and refluxed for 4 hours. After the indicated time, the reaction was cooled down to room temperature and was neutralized with 6 N NaOH aqueous solution. The resulting mixture was extracted with dichloromethane (2 x 500 mL). The organic layers were combined, dried over Na2SO4, filtered, and concentrated. The residue was purified by chromatography on silica gel to afford the title product. Step 4 – Synthesis of 8-(disubstituted amino)quinoline-2-carbaldehyde (4-5) An oven-dried 250 mL round-bottomed flask equipped with a stir bar was charged with SeO2 (13.3 g, 120 mmol, 1.2 equiv), 1,4-dioxane/H2O (120 mL/1.2 mL). The mixture was stirred at 80 °C for 0.5 hour. Then (4-4) (100 mmol, 1.0 equiv) was added. The mixture was stirred at 80 °C for 3 hours. After the indicated time, the reaction was cooled down to room temperature and filtered, concentrated. The residue was purified by chromatography on silica gel to afford the title product. Step 5 – Synthesis of 2-(substituted phenyl)-5-(disubstituted amino)imidazo[1,5-a]quinoline-2- ium chloride (4-7) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with (4-5) (10 mmol, 1.0 equiv), (4-6) (10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and toluene (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 110 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product. The following compounds were prepared according to Step 3 of the general procedure: N,N-2-trimethylquinolin-8-amine (44). According to the general procedure, the title product was obtained in 55% yield. 1 H NMR (500 MHz, Chloroform-d) δ 7.99 (d, J = 8.3 Hz, 1H), 7.40 – 7.33 (m, 2H), 7.26 (d, J = 8.3 Hz, 1H), 7.14 – 7.06 (m, 1H), 3.13 (s, 6H), 2.80 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ 156.35, 149.84, 142.14, 136.48, 127.70, 125.64, 121.54, 120.52, 115.45, 25.77. N,N-diethyl-2-methylquinolin-8-amine (45). According to the general procedure, the title product was obtained in 58% yield. 1 H NMR (500 MHz, Chloroform-d) δ 7.96 (d, J = 8.4 Hz, 1H), 7.35 – 7.27 (m, 2H), 7.22 (d, J = 8.3 Hz, 1H), 7.10 – 7.04 (m, 1H), 3.57 (q, J = 7.0 Hz, 4H), 2.74 (s, 3H), 1.16 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 156.06, 147.07, 142.82, 136.45, 127.88, 125.32, 121.43, 119.99, 117.68, 46.78, 25.74, 12.06. HRMS calcd for C42H55N6 + (3M + H + ) 643.4483, found 643.4509. 2-methyl-8-(piperidin-1-yl)quinoline (46). According to the general procedure, the title product was obtained in 68% yield. 1 H NMR (500 MHz, Chloroform-d) δ 7.96 (d, J = 8.3 Hz, 1H), 7.39 – 7.31 (m, 2H), 7.22 (d, J = 8.4 Hz, 1H), 7.10 (dd, J = 6.5, 2.5 Hz, 1H), 3.33 (t, J = 5.3 Hz, 4H), 2.74 (s, 3H), 1.91 (p, J = 5.6 Hz, 4H), 1.67 (q, J = 6.2 Hz, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 156.46, 150.06, 142.19, 136.49, 127.68, 125.74, 121.37, 120.80, 115.86, 53.66, 26.21, 25.91, 24.75. HRMS calcd for C 3 0H36KN4 + (2M + K + ) 491.2572, found 491.2587. 4-(2-methylquinolin-8-yl)morpholine (47). According to the general procedure, the title product was obtained in 66% yield. 1 H NMR (500 MHz, Chloroform-d) δ 7.99 (d, J = 8.4 Hz, 1H), 7.43 – 7.34 (m, 2H), 7.25 (d, J = 8.4 Hz, 1H), 7.09 (dd, J = 6.9, 2.1 Hz, 1H), 4.08 – 4.02 (m, 4H), 3.43 (t, J = 4.6 Hz, 4H), 2.73 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 156.80, 148.44, 141.87, 136.68, 127.76, 125.75, 121.65, 121.62, 115.63, 67.20, 52.55, 25.85. HRMS calcd for C 42 H 49 N 6 O 3 + (3M + H + ) 685.3861, found 685.3896. The following compounds were prepared according to Step 4 of the general procedure: 8-(dimethylamino)quinoline-2-carbaldehyde (48). According to the general procedure, the title product was obtained in 75% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.24 (d, J = 0.9 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 8.00 (d, J = 8.4 Hz, 1H), 7.56 (t, J = 7.9 Hz, 1H), 7.41 (dd, J = 8.2, 1.3 Hz, 1H), 7.17 – 7.11 (m, 1H), 3.22 (s, 6H). 8-(diethylamino)quinoline-2-carbaldehyde (49). According to the general procedure, the title product was obtained in 78% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.21 (d, J = 0.9 Hz, 1H), 8.21 – 8.16 (m, 1H), 7.96 (d, J = 8.4 Hz, 1H), 7.52 (t, J = 7.9 Hz, 1H), 7.31 (dd, J = 8.0, 1.2 Hz, 1H), 7.10 (dd, J = 7.8, 1.3 Hz, 1H), 3.67 (q, J = 7.0 Hz, 4H), 1.28 (t, J = 7.0 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 193.79, 149.52, 148.76, 142.13, 137.56, 132.09, 129.65, 118.48, 116.84, 116.47, 47.02, 12.54. HRMS calcd for C 14 H 17 N 2 O + (M + H + ) 229.1335, found 229.1338. 8-(piperidin-1-yl)quinoline-2-carbaldehyde (50). According to the general procedure, the title product was obtained in 85% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.19 (s, 1H), 8.24 (d, J = 8.4 Hz, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.56 (t, J = 7.9 Hz, 1H), 7.44 (d, J = 8.1 Hz, 1H), 7.20 (d, J = 7.6 Hz, 1H), 3.42 (t, J = 5.4 Hz, 4H), 1.94 (p, J = 5.7 Hz, 4H), 1.71 (p, J = 5.9 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 194.00, 151.51, 150.05, 142.25, 137.81, 131.75, 129.84, 120.51, 116.94, 116.74, 53.76, 26.18, 24.59. HRMS calcd for C 45 H 49 N 6 O 3 + (M + H + ) 721.3861, found 721.3900. 8-morpholinoquinoline-2-carbaldehyde (51). According to the general procedure, the title product was obtained in 71% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.13 (d, J = 0.9 Hz, 1H), 8.21 (dd, J = 8.4, 0.9 Hz, 1H), 7.96 (d, J = 8.4 Hz, 1H), 7.54 (t, J = 7.9 Hz, 1H), 7.45 (dd, J = 8.1, 1.3 Hz, 1H), 7.15 (dd, J = 7.6, 1.3 Hz, 1H), 4.05 – 4.00 (m, 4H), 3.49 – 3.43 (m, 4H). 13 C NMR (126 MHz, CDCl3) δ 193.48, 150.19, 149.93, 141.92, 138.02, 131.71, 129.78, 121.42, 117.11, 116.54, 67.06, 52.54. HRMS calcd for C 2 8H29N4O4 + (M + H + ) 485.2183, found 485.2196. The following compounds were prepared according to Step 5 of the general procedure: 2-(2,6-diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-2-ium chloride (52). According to the general procedure, the title product was obtained in 88% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.56 (d, J = 1.8 Hz, 1H), 9.10 (d, J = 1.9 Hz, 1H), 8.58 (d, J = 9.6 Hz, 1H), 7.72 (dq, J = 6.6, 3.4, 2.9 Hz, 3H), 7.67 – 7.60 (m, 2H), 7.40 (d, J = 7.8 Hz, 2H), 2.79 (s, 6H), 2.26 (p, J = 6.8 Hz, 2H), 1.26 (d, J = 6.8 Hz, 6H), 1.18 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 163.74, 145.59, 145.29, 132.22, 131.40, 130.71, 129.66, 129.29, 127.75, 127.61, 126.70, 124.80, 124.36, 123.19, 119.12, 117.89, 44.82, 28.80, 24.73, 24.17. HRMS calcd for C 2 5H30N3 + (M – Cl-) 372.2434, found 372.2456. 9-(diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]quin olin-2-ium chloride (53). According to the general procedure, the title product was obtained in 85% yield. 1 H NMR (500 MHz, Chloroform-d) δ 11.01 (s, 1H), 8.18 (s, 1H), 7.88 (d, J = 9.6 Hz, 1H), 7.78 – 7.61 (m, 5H), 7.40 (d, J = 7.9 Hz, 2H), 3.19 (dq, J = 13.9, 7.0 Hz, 2H), 3.08 (dq, J = 14.1, 7.2 Hz, 2H), 2.22 (p, J = 6.8 Hz, 2H), 1.19 (dd, J = 21.0, 6.8 Hz, 12H), 0.96 (t, J = 7.1 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 145.22, 141.77, 132.39, 131.20, 130.37, 130.00, 129.42, 128.63, 127.38, 127.35, 127.23, 126.74, 124.87, 117.33, 115.88, 48.98, 28.76, 24.55, 23.89, 11.55. HRMS calcd for C 2 7H34N3 + (M – Cl-) 400.2747, found 400.2760. 2-(2,6-diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]qu inolin-2-ium chloride (54). According to the general procedure, the title product was obtained in 87% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.79 – 10.67 (m, 1H), 8.94 (d, J = 1.8 Hz, 1H), 8.43 (d, J = 9.6 Hz, 1H), 7.63 (s, 3H), 7.54 (q, J = 9.3, 8.6 Hz, 2H), 7.30 (d, J = 7.9 Hz, 2H), 2.96 (d, J = 11.7 Hz, 2H), 2.81 (t, J = 10.9 Hz, 2H), 2.13 (p, J = 6.8 Hz, 2H), 1.75 (dd, J = 9.8, 6.1 Hz, 3H), 1.40 – 1.28 (m, 3H), 1.14 (d, J = 6.7 Hz, 6H), 1.05 (d, J = 6.7 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 145.28, 145.08, 132.29, 131.34, 130.47, 129.79, 129.16, 127.81, 127.48, 126.77, 124.75, 124.27, 124.03, 118.87, 117.43, 54.10, 28.74, 26.18, 24.65, 23.97, 23.22. HRMS calcd for C 28 H 34 N 3 + (M – Cl-) 412.2747, found 412.2757. 2-(2,6-diisopropylphenyl)-9-morpholinoimidazo[1,5-a]quinolin -2-ium chloride (55). According to the general procedure, the title product was obtained in 76% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.88 (s, 1H), 9.00 (s, 1H), 8.44 (d, J = 9.4 Hz, 1H), 7.81 – 7.73 (m, 3H), 7.61 (dd, J = 8.8, 6.8 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H), 3.94 (dd, J = 11.8, 2.7 Hz, 2H), 3.53 (t, J = 11.4 Hz, 2H), 3.18 (td, J = 11.8, 2.9 Hz, 2H), 2.91 (d, J = 11.8 Hz, 2H), 2.17 (q, J = 6.7 Hz, 2H), 1.17 (d, J = 6.6 Hz, 6H), 1.10 (d, J = 6.7 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 144.94, 143.52, 132.33, 131.36, 130.27, 130.04, 128.71, 127.80, 127.56, 127.54, 124.72, 124.34, 124.29, 118.91, 117.29, 66.60, 52.99, 28.64, 24.61, 23.92. HRMS calcd for C 2 7H32N3 + (M – Cl-) 414.2540, found 414.2546. 9-(dimethylamino)-2-mesitylimidazo[1,5-a]quinolin-2-ium chloride (56). According to the general procedure, the title product was obtained in 84% yield. 1 H NMR (500 MHz, Chloroform-d) δ 10.53 (d, J = 1.8 Hz, 1H), 8.94 (d, J = 1.8 Hz, 1H), 8.34 (d, J = 9.6 Hz, 1H), 7.67 – 7.60 (m, 3H), 7.51 (d, J = 9.6 Hz, 1H), 7.05 (s, 2H), 2.75 (s, 6H), 2.35 (s, 3H), 2.06 (s, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 145.64, 141.68, 134.18, 131.31, 131.29, 129.95, 129.59, 129.24, 127.48, 127.34, 126.24, 124.22, 122.93, 117.89, 117.36, 44.66, 21.18, 17.65. HRMS calcd for C 2 2H24N3 + (M – Cl-) 330.1965, found 330.1978. Example 5: Synthesis of Imidazo[1,5-α]quinoline NHC Ligand-Metal Complexes Synthesis of 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene silver(I) chloride (57) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (52) (122 mg, 0.3 mmol, 1.0 equiv), Ag2O (83.4 mg, 0.36 mmol, 1.2 equiv), NaCl (35 mg, 0.6 mmol, 2.0 equiv), KCl (45 mg, 0.6 mmol, 2.0 equiv) and 4Å MS (240 mg). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Anhydrous THF (4.0 mL) was added and the reaction mixture was stirred at 90 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a grown solid (125 mg, 81%). 1 H NMR (500 MHz, Chloroform-d) δ 7.50 (d, J = 7.8 Hz, 1H), 7.47 – 7.40 (m, 2H), 7.39 – 7.28 (m, 5H), 7.23 (d, J = 9.4 Hz, 1H), 2.76 (s, 6H), 2.35 (p, J = 6.9 Hz, 2H), 1.30 (d, J = 6.9 Hz, 6H), 1.15 (d, J = 6.9 Hz, 6H).13C NMR (126 MHz, CDCl3) δ 185.78 (d, J = 18.6 Hz), 183.71 (d, J = 18.7 Hz), 145.54, 145.32, 137.18, 135.95, 131.95 (d, J = 7.2 Hz), 130.52, 128.10, 127.06, 126.41, 126.31, 124.15, 123.55, 123.01, 120.30, 115.23, 114.37 (d, J = 6.8 Hz), 44.34, 28.35, 24.65, 24.38. HRMS calcd for C 2 5H29AgN3 + (M – Cl-) 478.1407, found 478.1395. Synthesis of 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quin olin-3-ylidene silver(I) chloride (58) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (53) (131 mg, 0.3 mmol, 1.0 equiv), Ag 2 O (83.4 mg, 0.36 mmol, 1.2 equiv), NaCl (35 mg, 0.6 mmol, 2.0 equiv), KCl (45 mg, 0.6 mmol, 2.0 equiv) and 4Å MS (240 mg). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Anhydrous THF (4.0 mL) was added and the reaction mixture was stirred at 90 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a grown solid (143 mg, 88%). 1 H NMR (500 MHz, Chloroform-d) δ 7.50 (t, J = 7.8 Hz, 1H), 7.45 (dd, J = 8.1, 7.3 Hz, 1H), 7.39 (ddd, J = 9.1, 7.7, 1.9 Hz, 2H), 7.33 (d, J = 1.7 Hz, 1H), 7.29 (d, J = 7.8 Hz, 2H), 7.26 (s, 1H), 7.21 (d, J = 9.4 Hz, 1H), 3.26 (dt, J = 13.7, 6.8 Hz, 2H), 3.16 (dq, J = 13.1, 7.2 Hz, 2H), 2.32 (p, J = 6.9 Hz, 2H), 1.29 (d, J = 6.9 Hz, 6H), 1.16 – 1.08 (m, 12H). 13 C NMR (126 MHz, CDCl 3 ) δ 186.53 (d, J = 18.4 Hz), 184.47 (d, J = 18.6 Hz), 145.60, 141.03, 136.09, 132.12 (d, J = 7.3 Hz), 130.69, 128.64, 128.34, 126.64, 126.40, 124.84, 124.46, 124.27, 115.08, 114.34 (d, J = 6.7 Hz), 47.55, 28.46, 24.80, 24.35, 11.56. HRMS calcd for C 27 H 33 AgN 3 + (M – Cl-) 506.1720, found 506.1706. Synthesis of 2-(2,6-Diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]qu inolin-3-ylidene silver(I) chloride (59) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (54) (134 mg, 0.3 mmol, 1.0 equiv), Ag2O (83.4 mg, 0.36 mmol, 1.2 equiv), NaCl (35 mg, 0.6 mmol, 2.0 equiv), KCl (45 mg, 0.6 mmol, 2.0 equiv) and 4Å MS (240 mg). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Anhydrous THF (4.0 mL) was added and the reaction mixture was stirred at 90 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH 2 Cl 2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a grown solid (152 mg, 91%). 1 H NMR (500 MHz, Chloroform-d) δ 7.42 (s, 1H), 7.39 – 7.33 (m, 2H), 7.27 – 7.15 (m, 5H), 7.11 (d, J = 9.4 Hz, 1H), 3.35 – 3.25 (m, 2H), 2.47 (td, J = 11.6, 2.5 Hz, 2H), 2.34 – 2.15 (m, 4H), 1.74 – 1.64 (m, 1H), 1.59 (d, J = 13.7 Hz, 2H), 1.22 (d, J = 6.8 Hz, 7H), 1.02 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 186.12 (d, J = 18.4 Hz), 184.06 (d, J = 18.5 Hz), 145.58, 135.96, 131.67 (d, J = 6.8 Hz), 130.52, 128.09, 127.14, 126.51, 126.16, 126.15, 124.14, 123.38, 120.08, 114.86, 114.71 (d, J = 6.9 Hz), 53.11, 28.37, 25.84, 25.60, 23.78, 23.53. HRMS calcd for C 2 9H33AgN3Cl + (M + H + ) 554.1487, found 554.1435. Synthesis of 2-(2,6-diisopropylphenyl)-9-(morpholin -4-yl)imidazo[1,5-a]quinolin-3-ylidene silver(I) chloride (60) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (55) (135 mg, 0.3 mmol, 1.0 equiv), Ag 2 O (83.4 mg, 0.36 mmol, 1.2 equiv), NaCl (35 mg, 0.6 mmol, 2.0 equiv), KCl (45 mg, 0.6 mmol, 2.0 equiv) and 4Å MS (240 mg). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Anhydrous THF (4.0 mL) was added and the reaction mixture was stirred at 90 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a grown solid (155 mg, 93%). 1 H NMR (500 MHz, Chloroform-d) δ 7.50 (dt, J = 14.3, 7.8 Hz, 2H), 7.41 (ddd, J = 11.1, 7.8, 1.6 Hz, 2H), 7.35 – 7.27 (m, 4H), 7.23 (d, J = 9.4 Hz, 1H), 4.38 (td, J = 11.6, 2.1 Hz, 2H), 3.88 – 3.76 (m, 2H), 3.27 – 3.15 (m, 2H), 2.84 (td, J = 11.6, 3.1 Hz, 2H), 2.31 (p, J = 6.8 Hz, 2H), 1.29 (d, J = 6.9 Hz, 6H), 1.10 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 185.59 (d, J = 18.5 Hz), 183.54 (d, J = 18.5 Hz), 145.45, 144.27, 135.73, 131.86 (d, J = 6.8 Hz), 130.68, 128.32, 127.41, 126.50, 126.48, 126.01, 125.99, 124.24, 124.13, 119.68, 115.14, 115.12, 114.94 (d, J = 6.9 Hz), 66.55, 51.70, 28.43, 25.41, 23.59. HRMS calcd for C 27 H 31 AgN 3 O + (M – Cl-) 520.1513, found 520.1540. Synthesis of 2-(2,4,6-trimethylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene silver(I) chloride (61) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (56) (110 mg, 0.3 mmol, 1.0 equiv), Ag 2 O (83.4 mg, 0.36 mmol, 1.2 equiv), NaCl (35 mg, 0.6 mmol, 2.0 equiv), KCl (45 mg, 0.6 mmol, 2.0 equiv) and 4Å MS (240 mg). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Anhydrous THF (4.0 mL) was added and the reaction mixture was stirred at 90 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a grown solid (121 mg, 85%). 1 H NMR (500 MHz, Chloroform-d) δ 7.44 – 7.37 (m, 2H), 7.33 – 7.24 (m, 3H), 7.17 (d, J = 9.4 Hz, 1H), 7.00 (s, 2H), 2.75 (s, 6H), 2.36 (s, 3H), 2.02 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 185.47 (d, J = 18.6 Hz), 183.40 (d, J = 18.8 Hz), 145.37, 139.56, 136.66, 134.49, 132.12 (d, J = 7.1 Hz), 129.54, 129.49, 128.00, 126.99, 126.30, 126.13, 126.11, 123.34, 120.21, 115.16, 115.14, 113.06 (d, J = 6.8 Hz), 44.32, 21.15, 17.92. HRMS calcd for C 2 2H23AgN3 + (M – Cl-) 436.0937, found 436.0946. Synthesis of 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene gold(I) chloride (62) An oven-dried flask equipped with a stir bar was charged with the corresponding NHCAgCl salt (52) (154 mg, 0.3 mmol, 1.0 equiv), DCM (4 mL) and AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) was added. The mixture was stirred at room temperature for 16 hours. The solution was filtered and concentrated. The residue was purified by chromatography on silica gel to afford the title product (172 mg, 95%). 1 H NMR (500 MHz, Chloroform-d) δ 7.51 (t, J = 7.8 Hz, 1H), 7.41 (t, J = 7.8 Hz, 1H), 7.35 – 7.26 (m, 4H), 7.24 (d, J = 9.1 Hz, 2H), 7.18 (d, J = 9.4 Hz, 1H), 2.71 (s, 6H), 2.38 (p, J = 6.9 Hz, 2H), 1.35 (d, J = 6.8 Hz, 6H), 1.15 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 174.39, 145.48, 145.45, 135.57, 131.36, 130.54, 128.48, 127.25, 126.57, 124.62, 124.11, 121.87, 120.43, 114.86, 114.09, 42.76, 28.50, 24.65, 24.14. HRMS calcd for C 2 5H30AuClN3 (M + H + ) 604.1788, found 604.1815. Synthesis of 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quin olin-3-ylidene gold(I) chloride (63) An oven-dried flask equipped with a stir bar was charged with the corresponding NHCAgCl salt (53) (163 mg, 0.3 mmol, 1.0 equiv), DCM (4 mL) and AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) was added. The mixture was stirred at room temperature for 16 hours. The solution was filtered and concentrated. The residue was purified by chromatography on silica gel to afford the title product (152 mg, 80%). 1 H NMR (500 MHz, Chloroform-d) δ 7.43 (t, J = 7.8 Hz, 1H), 7.33 (t, J = 7.8 Hz, 1H), 7.26 – 7.14 (m, 5H), 7.14 – 7.06 (m, 2H), 3.23 (dd, J = 13.6, 6.9 Hz, 2H), 2.97 (dd, J = 13.6, 7.0 Hz, 2H), 2.28 (p, J = 6.8 Hz, 2H), 1.26 (d, J = 6.9 Hz, 6H), 1.08 – 1.00 (m, 12H). 13 C NMR (126 MHz, CDCl 3 ) δ 174.84, 145.45, 142.08, 135.64, 131.40, 13055 12859 12673 12671 12668 12608 12411 12396 12229 11461 11459 11398 45.53, 28.53, 24.67, 24.06, 11.03. HRMS calcd for C 2 7H33AuClN3Na + (M + Na + ) 654.1921, found 654.1950. Synthesis of 2-(2,6-diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]qu inolin-3-ylidene gold(I) chloride (64) An oven-dried flask equipped with a stir bar was charged with the corresponding NHCAgCl salt (54) (167 mg, 0.3 mmol, 1.0 equiv), DCM (4 mL) and AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) was added. The mixture was stirred at room temperature for 16 hours. The solution was filtered and concentrated. The residue was purified by chromatography on silica gel to afford the title product (164 mg, 85%). 1 H NMR (500 MHz, Chloroform-d) δ 7.52 (t, J = 7.8 Hz, 1H), 7.46 – 7.36 (m, 2H), 7.30 (t, J = 6.1 Hz, 3H), 7.24 (dd, J = 7.2, 1.7 Hz, 1H), 7.18 (q, J = 9.4 Hz, 2H), 3.33 (d, J = 11.8 Hz, 2H), 2.73 (d, J = 12.0 Hz, 2H), 2.42 (p, J = 6.9 Hz, 2H), 2.31 (q, J = 11.7 Hz, 2H), 1.77 (dt, J = 13.3, 4.4 Hz, 1H), 1.59 (d, J = 12.5 Hz, 2H), 1.35 (d, J = 6.8 Hz, 7H), 1.12 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 174.61, 145.93, 145.52, 135.54, 131.13, 130.53, 128.46, 127.39, 126.63, 124.71, 124.14, 121.86, 120.48, 114.50, 114.40, 52.25, 28.49, 25.41, 24.77, 24.24, 23.54. HRMS calcd for C 2 8H34AuClN3 + (M + H + ) 644.2101, found 644.2109. Synthesis of 2-(2,6-diisopropylphenyl)-9-(morpholin -4-yl)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride (65) An oven-dried flask equipped with a stir bar was charged with the corresponding NHCAgCl salt (55) (167 mg, 0.3 mmol, 1.0 equiv), DCM (4 mL) and AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) was added. The mixture was stirred at room temperature for 16 hours. The solution was filtered and concentrated. The residue was purified by chromatography on silica gel to afford the title product (178 mg, 92%). 1 H NMR (500 MHz, Chloroform-d) δ 7.50 (dt, J = 23.9, 7.8 Hz, 2H), 7.39 – 7.27 (m, 5H), 7.25 – 7.16 (m, 2H), 4.51 (t, J = 11.2 Hz, 2H), 3.76 (d, J = 11.4 Hz, 2H), 3.15 (d, J = 11.6 Hz, 2H), 2.92 (t, J = 11.4 Hz, 2H), 2.34 (p, J = 6.9 Hz, 2H), 1.33 (d, J = 6.9 Hz, 6H), 1.11 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 174.52, 145.38, 144.79, 135.36, 131.31, 130.66, 128.66, 127.69, 126.56, 124.87, 124.19, 123.12, 119.99, 114.92, 114.73, 65.67, 50.94, 28.56, 25.33, 23.52. HRMS calcd for C 2 7H32AuClN3O + (M + H + ) 646.1894, found 646.1911. Synthesis of 2-(2,4,6-trimethylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene gold(I) chloride (66) An oven-dried flask equipped with a stir bar was charged with the corresponding NHCAgCl salt (56) (142 mg, 0.3 mmol, 1.0 equiv), DCM (4 mL) and AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) was added. The mixture was stirred at room temperature for 16 hours. The solution was filtered and concentrated. The residue was purified by chromatography on silica gel to afford the title product (145 mg, 86%). 1 H NMR (500 MHz, Chloroform-d) δ 7.28 (t, J = 7.9 Hz, 1H), 7.19 (d, J = 3.5 Hz, 2H), 7.14 – 7.08 (m, 2H), 7.03 (d, J = 9.4 Hz, 1H), 6.88 (s, 2H), 2.59 (s, 6H), 2.24 (s, 3H), 1.95 (s, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 172.50, 144.35, 138.41, 135.23, 133.42, 130.53, 128.29, 127.37, 126.12, 125.17, 123.46, 120.70, 119.17, 113.92, 111.87, 41.74, 20.15, 17.03. HRMS calcd for C 2 2H24AuClN3 + (M + H + ) 562.1324, found 562.1340. Example 6: Synthesis of Aryl Substituted Imidazo[1,5-α]quinoline N-Heterocyclic Carbene (NHC) Ligands Synthesis of 8-mesityl-2-methylquinoline (67) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 8-bromo-2-methylquinoline (2.22 g, 10 mmol, 1.0 equiv), Ni(PCy3)Cl2 (138 mg, 0.2 mmol) and anhydrous THF (20 mL) under argon protection. Then 2-mesitylmagnesium bromide solution (15 mL, 1.0 M in THF, 15 mmol, 1.5 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 95 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and quenched by water. The mixture was diluted with EtOAc (50 mL), washed with H 2 O (1 x 20 mL) and brine (1 x 20 mL). The organic layers were combined, dried, filtered, and concentrated. The residue was purified by chromatography on silica gel to afford the title product (2.48 g, 95%). 1 H NMR (500 MHz, Chloroform-d) δ 8.07 (d, J = 8.4 Hz, 1H), 7.79 (dd, J = 8.1, 1.6 Hz, 1H), 7.54 (dd, J = 8.0, 7.0 Hz, 1H), 7.48 (dd, J = 7.0, 1.7 Hz, 1H), 7.26 (d, J = 8.3 Hz, 1H), 7.03 (s, 2H), 2.61 (s, 3H), 2.42 (s, 3H), 1.95 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 158.71, 146.30, 139.93, 137.31, 136.70, 136.21, 136.04, 130.62, 127.84, 126.93, 126.75, 125.27, 121.77, 25.80, 21.26, 20.83. HRMS calcd for C 1 9H19NNa + (M + Na + ) 284.1410, found 284.1420. S An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with SeO 2 (1.33 g, 12 mmol, 1.2 equiv), 1,4-dioxane/H 2 O (30 mL/0.3 mL). The mixture was stirred at 80 °C for 0.5 hour. Then 8-mesityl-2-methylquinoline (67) (10 mmol, 1.0 equiv) was added. The mixture was stirred at 80 °C for 3 hours. After the indicated time, the reaction was cooled down to room temperature and filtered, concentrated. The residue was purified by chromatography on silica gel to afford the title product (17 g 62%) 1 H NMR (500 MHz Chloroform-d) δ 997 (d J = 0.9 Hz, 1H), 8.35 (dd, J = 8.4, 0.9 Hz, 1H), 8.02 (d, J = 8.4 Hz, 1H), 7.92 (dd, J = 8.2, 1.5 Hz, 1H), 7.74 (dd, J = 8.2, 7.0 Hz, 1H), 7.62 (dd, J = 7.0, 1.5 Hz, 1H), 7.02 (s, 2H), 2.41 (s, 3H), 1.90 (s, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 194.57, 152.46, 146.30, 141.99, 137.56, 136.85, 136.49, 135.95, 131.70, 130.37, 129.03, 127.96, 127.22, 117.06, 21.20, 20.70. HRMS calcd for C 3 8H34N2NaO2 + (2M + Na + ) 573.2512, found 573.2537. Synthesis of 2-(2,6-Diisopropylphenyl)-9-(2,4,6-trimethylphenyl)imidazo[1 ,5-a]quinolin-2-ium chloride (69) An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 8-mesitylquinoline-2-carbaldehyde (68) (10 mmol, 1.0 equiv), 2,6-diisopropylaniline (10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and toluene (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 110 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (3.7 g, 76%). 1 H NMR (500 MHz, Chloroform-d) δ 8.32 (s, 1H), 8.04 (d, J = 9.6 Hz, 1H), 7.99 (dd, J = 7.9, 1.6 Hz, 1H), 7.84 (t, J = 7.6 Hz, 1H), 7.74 (d, J = 9.2 Hz, 1H), 7.55 (t, J = 7.8 Hz, 1H), 7.49 (dd, J = 7.4, 1.6 Hz, 1H), 7.27 (d, J = 8.0 Hz, 2H), 6.99 (s, 2H), 2.24 (s, 3H), 1.96 (p, J = 6.8 Hz, 2H), 1.86 (s, 6H), 1.15 (d, J = 6.7 Hz, 6H), 0.93 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 144.82, 140.44, 135.83, 133.84, 132.55, 132.27, 131.62, 131.01, 130.06, 129.98, 129.90, 128.75, 127.04, 126.97, 126.83, 124.60, 118.27, 116.45, 28.61, 24.65, 23.10, 21.08, 20.21. HRMS calcd for C 3 2H35N2 + (M – Cl-) 447.2795, found 447.2833. Example 7: Synthesis of Aryl Substituted Imidazo[1,5-α]quinoline NHC Ligand-Metal Complexes Synthesis of 2-(2,6-Diisopropylphenyl)-9-(2,4,6-trimethylphenyl)imidazo[1 ,5-a]quinolin-3- ylidene gold(I) chloride (70) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (69) (145 mg, 0.3 mmol, 1.0 equiv), AuClSMe2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 mL, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was was purified by chromatography on silica gel to afford the title product (112 mg, 55%). 1 H NMR (500 MHz, Chloroform-d) δ 7.64 (dd, J = 7.6, 1.6 Hz, 1H), 7.56 (t, J = 7.6 Hz, 1H), 7.42 (ddd, J = 7.8, 4.9, 3.2 Hz, 2H), 7.30 – 7.26 (m, 2H), 7.23 (d, J = 9.3 Hz, 1H), 7.19 (d, J = 7.8 Hz, 2H), 6.92 (s, 2H), 2.29 – 2.22 (m, 5H), 1.97 (s, 6H), 1.18 (d, J = 6.8 Hz, 6H), 1.08 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 145.12, 137.44, 135.48, 134.99, 130.53, 130.30, 127.86, 127.49, 126.68, 126.50, 124.09, 114.74, 114.60, 28.45, 24.80, 23.81, 21.49. HRMS calcd for C 3 2H34AuClN2Na + (M + Na + ) 701.1968, found 701.1987. Example 8: Synthesis of Control NHC Ligands and Ligand-Metal Complexes S An oven-dried 100 mL round-bottomed flask equipped with a stir bar was charged with 2-(1,3-dioxolan-2-yl)-6-isopropylpyridine (1.93 g, 10 mmol, 1.0 equiv), 2,6-diisopropylaniline (1.77 g, 10 mmol, 1.0 equiv), paraformaldehyde (450 mg, 15 mmol, 1.5 equiv) and EtOH (25 mL). HCl (4.0 M in dioxane, 5.0 mL, 2.0 equiv) was added dropwise into the reaction at room temperature. The mixture was stirred at 70 °C for 24 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel (CH 2 Cl 2 /MeOH = 20/1) to afford the title product (2.14 g, 60%). 1 H NMR (500 MHz, CDCl3) δ 11.68 (s, 1H), 7.71 (d, J = 9.3 Hz, 1H), 7.69 (s, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.36 (d, J = 7.8 Hz, 2H), 7.34 – 7.31 (m, 1H), 7.00 (d, J = 7.0 Hz, 1H), 4.49 (s, 1H), 2.23 – 2.15 (m, 2H), 1.49 (d, J = 4.3 Hz, 6H), 1.34 (d, J = 6.6 Hz, 6H), 1.17 (d, J = 6.7 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 145.17, 145.03, 131.94, 130.89, 130.75, 129.31, 126.37, 124.56, 123.36, 115.41, 114.58, 112.88, 29.51, 28.89, 24.52, 24.39, 20.28. HRMS calcd for C 2 2H29N2 + (M – Cl-) 321.2325, found 321.2331. Synthesis of 2-(2,6-Diisopropylphenyl)-5-isopropylimidazo[1,5-a]pyridin-3 -ylidene gold(I) chloride (A3) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (A2) (107 mg, 0.3 mmol, 1.0 equiv), AuClSMe 2 (90 mg, 0.3 mmol, 1.0 equiv) and finely powdered K2CO3 (83 mg, 0.6 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (104 mg, 63%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.44 (t, J = 7.8 Hz, 1H), 7.30 – 7.17 (m, 4H), 6.93 (dd, J = 9.0, 7.1 Hz, 1H), 6.60 (d, J = 6.8 Hz, 1H), 5.24 (dq, J = 13.3, 6.6 Hz, 1H), 2.31 – 1.93 (m, 2H), 1.40 (d, J = 6.7 Hz, 6H), 1.25 (d, J = 6.8 Hz, 6H), 1.04 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 163.16, 147.34, 145.23, 135.77, 132.04, 130.75, 124.19, 123.48, 115.72, 113.67, 110.55, 30.37, 28.47, 24.58, 24.26, 22.14. HRMS calcd for C 2 2H28AuClN2Na + (M + + Na) 575.1499, found 575.1506. *The compound is ineffective in promoting Au(I)/(III) reactivity. An oven-dried 20 mL screw cap vial equipped with a magnetic stir bar was charged with 4-(dimethylamino)picolinaldehyde (750.9 mg, 5 mmol, 1.0 equiv), 2,6-diisopropylaniline (886.5 mg, 5 mmol, 1.0 equiv), Na 2 SO 4 (1.42 g, 10 mmol, 2.0 equiv), formic acid (46.0 mg, 1 mmol, 2.0 equiv) and 15 mL anhydrous MeOH. The reaction mixture was stirred at room temperature for 24 h. After the indicated time, the reaction was concentrated. The residue was purified by chromatography on silica gel to afford the title product (866.5 mg, 56%). 1 H NMR (500 MHz, CDCl 3 ) δ 8.35 (d, J = 5.9 Hz, 1H), 8.24 (s, 1H), 7.52 (d, J = 2.6 Hz, 1H), 7.13 (dt, J = 8.6, 6.8 Hz, 3H), 6.60 (dd, J = 5.9, 2.7 Hz, 1H), 3.07 (s, 6H), 3.00 (dd, J = 13.7, 6.9 Hz, 2H), 1.19 (d, J = 7.0 Hz, 12H). 13 C NMR (126 MHz, CDCl3) δ 164.06, 154.82, 154.28, 149.78, 148.59, 137.38, 124.33, 123.04, 108.34, 103.52, 39.29, 27.93, 23.58. HRMS calcd for C 20 H 28 N 3 + (M + + H) 310.2278, found 310.2280. S An oven-dried 50 mL screw cap vial equipped with a magnetic stir bar was charged with (E)-2-(((2,6-diisopropylphenyl)imino)methyl)-N,N-dimethylpyr idin-4-amine (618.9 mg, 2.0 mmol, 1.0 equiv), paraformaldehyde (78.0 mg, 2.6 mmol, 1.3 equiv) and toluene (15 mL). TMSCl (434.5 mg, 4.0 mmol, 2.0 equiv) was added dropwise at room temperature and the reaction mixture was stirred at 80 °C for 12 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel to afford the title product (237.6 mg, 35%). Isomer A: 1 H NMR (500 MHz, CDCl 3 ) δ 8.77 (s, 1H), 8.23 (d, J = 6.0 Hz, 1H), 7.31 (dd, J = 16.0, 8.2 Hz, 1H), 7.15 (d, J = 7.7 Hz, 2H), 6.43 – 6.37 (m, 1H), 6.08 (d, J = 2.5 Hz, 1H), 4.56 (s, 2H), 2.89 (s, 6H), 2.83 (dq, J = 14.5, 7.1 Hz, 2H), 1.12 (d, J = 6.8 Hz, 6H), 0.95 (d, J = 6.8 Hz, 6H). Isomer B: 1 H NMR (500 MHz, CDCl3) δ 8.15 (s, 1H), 8.06 (d, J = 6.0 Hz, 1H), 7.31 (dd, J = 16.0, 8.2 Hz, 1H), 7.15 (d, J = 7.7 Hz, 2H), 6.79 (d, J = 2.5 Hz, 1H), 6.43 – 6.37 (m, 1H), 4.80 (s, 2H), 2.99 (s, 6H), 2.83 (dq, J = 14.5, 7.1 Hz, 2H), 1.09 (d, J = 6.9 Hz, 6H), 1.00 (d, J = 6.8 Hz, 6H). 13 C NMR (isomers A and B) (126 MHz, CDCl3) δ 163.55, 155.94, 155.01, 154.77, 154.69, 149.82, 148.82, 147.66, 146.61, 135.72, 134.17, 129.31, 128.77, 124.31, 124.10, 107.33, 106.72, 105.89, 105.83, 57.74, 53.86, 39.19, 39.07, 28.69, 28.40, 25.43, 24.94, 23.53, 23.25. HRMS calcd for C 21 H 30 N 3 O + (M + + H) 340.2383, found 340.2387. Synthesis of 2-(2,6-Diisopropylphenyl)-7-(dimethylamino)imidazo[1,5-a]pyr idin-2-ium chloride (A4) An oven-dried 10 mL screw cap vial equipped with a magnetic stir bar was charged with N-(2,6-diisopropylphenyl)-N-((4-(dimethylamino)pyridin-2-yl) methyl)formamide (169.7 mg, 0.5 mmol, 1.0 equiv) and toluene (5 mL). Phosphoryl chloride (84.3 mg, 0.55 mmol, 1.1 equiv) was added dropwise at room temperature and the reaction mixture was stirred at 80 °C for 12 hours. After the indicated time, the reaction was cooled down to room temperature and concentrated. The residue was purified by chromatography on silica gel to afford the title product (75.2 mg, 42%). 9 1 H NMR (500 MHz, CDCl3) δ 9.88 (s, 1H), 9.01 (d, J = 7.8 Hz, 1H), 7.52 (t, J = 7.8 Hz, 1H), 7.29 (d, J = 7.8 Hz, 2H), 7.05 (s, 1H), 7.00 – 6.89 (m, 1H), 6.34 (s, 1H), 3.08 (s, 6H), 2.19 (dt, J = 13.5, 6.8 Hz, 2H), 1.17 (d, J = 6.8 Hz, 6H), 1.13 (d, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 146.60, 145.17, 133.38, 131.70, 130.87, 125.87, 125.58, 124.45, 111.39, 108.42, 88.34, 40.14, 28.56, 24.51, 24.44. HRMS calcd for C 2 1H28N3 + (M – Cl-) 322.2278, found 322.2283. Synthesis of 2-(2,6-Diisopropylphenyl)-7-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene gold(I) chloride (A5) An oven-dried flask equipped with a stir bar was charged with the corresponding NHC ^HCl salt (A4) (71.6 mg, 0.2 mmol, 1.0 equiv), AuClSMe2 (58.9 mg, 0.2 mmol, 1.0 equiv) and finely powdered K2CO3 (55.2 mg, 0.4 mmol, 2.0 equiv). The reaction mixture was placed under a positive pressure of argon and subjected to three evacuation/backfilling cycles under high vacuum. Acetone (6.0 ml, 0.05 M) was added and the reaction mixture was stirred at 60 °C for 16 h. After the indicated time, the reaction mixture was diluted with CH2Cl2 (10 mL) and filtered. The solution was collected and concentrated. The title product was obtained by trituration from hexanes as a white solid (80.8 mg, 73%). 1 H NMR (500 MHz, CDCl 3 ) δ 8.44 (d, J = 8.0 Hz, 1H), 7.48 (t, J = 7.8 Hz, 1H), 7.26 (d, J = 7.9 Hz, 2H), 6.79 (s, 1H), 6.65 (dd, J = 8.0, 2.4 Hz, 1H), 6.14 (s, 1H), 3.04 (s, 6H), 2.30 (dt, J = 13.6, 6.8 Hz, 2H), 1.28 (d, J = 6.8 Hz, 6H), 1.11 (d, J = 6.9 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 162.03, 145.81, 145.49, 134.77, 132.37, 130.42, 128.13, 124.06, 108.38, 108.28, 89.15, 40.22, 28.31, 24.63, 24.50. HRMS calcd for C 2 1H27AuClN3Na+ (M + + Na) 576.1451, found 576.1457. *The compound is ineffective in promoting Au(I)/(III) reactivity. Synthesis of (2-(2,6-Diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]py ridin-3- ylidene)(2,2’-biphenyl) gold(III) chloride (A6) To a mixture of the corresponding Au(NHC)Cl (16) (55.4 mg, 0.1 mmol, 1.0 equiv) and AgSbF6 (38 mg, 0.11 mmol, 1.0 equiv) was added CH2Cl2 (5 mL) at room temperature and the resulting mixture was stirred for 15 min. After the indicated time, the reaction mixture was passed through glass fiber to remove AgCl, followed by addition of biphenylene (34.2 mg, 0.225 mmol, 2.25 equiv). After stirring at room temperature for 3 h, tetrabutylammonium chloride (34.7 mg, 0.125 mmol, 1.25 equiv) was added and the stirring was continued for 3 h. The title product was purified by chromatography on silica gel as a yellow solid (55 mg, 78%). 1 H NMR (500 MHz, CDCl3) δ 8.09 (dd, J = 7.6, 1.0 Hz, 1H), 7.44 (s, 1H), 7.41 (t, J = 7.8 Hz, 1H), 7.31 (ddd, J = 9.3, 6.5, 2.9 Hz, 4H), 7.10 (ddd, J = 16.3, 7.7, 1.2 Hz, 2H), 7.05 – 6.96 (m, 3H), 6.58 (td, J = 7.6, 1.4 Hz, 1H), 6.34 (d, J = 6.3 Hz, 1H), 6.10 (d, J = 7.2 Hz, 1H), 2.87 (s, 3H), 2.54 (dtd, J = 34.2, 13.5, 6.7 Hz, 5H), 1.47 (d, J = 6.6 Hz, 3H), 1.12 (d, J = 6.8 Hz, 3H), 0.91 (d, J = 6.9 Hz, 3H), 0.60 (d, J = 6.7 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ 175.44, 158.27, 153.87, 153.57, 153.33, 149.40, 146.58, 144.92, 134.82, 133.20, 132.92, 131.79, 130.68, 126.61, 126.38, 126.23, 126.19, 124.39, 124.04, 123.99, 121.08, 120.21, 117.09, 113.42, 104.77, 28.98, 28.32, 27.03, 26.05, 22.83, 21.86. HRMS calcd for C 3 3H35AuClN3Na + (M + + Na) 728.2077, found 728.2080. *The x-ray structure shows stabilizing effect of the C5 amino group on Au(III). Example 9: Characterization of NHC Ligands and Ligand-Metal Complexes Electronic characterization NHC-Se (1 complex) (A1) and NHC-Rh(I) complexes (38-40) were synthesized and characterized with regard to π-acceptance and σ-donation, respectively. The δ Se value of 214.65 ppm for (A1) (CDCl3) can be compared with IPr (δSe = 90 ppm), indicating much stronger π - accepting properties of this class of ligands. The avg. v CO = 2063.9 cm -1 for cationic 40 can be compared with cationic bis-NHC complex avg. v CO = 2057 cm -1 (Canac, JACS 2008, 130, 8406), indicating strong σ-donation of this class of ligands. One-bond CH J-values for coupling constants from 13 C satellites of the 1 H NMR spectrum (NHC salt) provide good indication of σ- donating properties of an NHC ligand. The value of 227.7 Hz for ligand (1) (CDCl 3 ) is consistent with this ligand being strongly σ -donating (cf., IPr: 1 JCH = 223.7 Hz). Complexation studies The complexation studies demonstrate that the ligands of the present disclosure are useful for the synthesis of well-defined, air and/or moisture stable complexes with Au(I), Ag(I), Cu(I), Pd(II), Rh(I) and Se. In certain embodiments, the cationic complexes are formed due to amine- to-metal coordination, and the complexes remain stable in a solid state, permitting their application in cationic catalysis. X-ray structural analysis The structures of several Au(I) complexes (FIGs.1-3) and representative Ag(I), Cu(I), and Pd(II) complexes have been fully characterized by x-ray analysis. The %buried volume (%Vbur) of 16 is 42.8%, which can be compared with (%Vbur) of 43.2% determined for 20; (%V bur ) of 47.8% determined for 18; (%V bur ) of 40.9% for 23 and (%V bur ) of 44.9% determined for 22. These values can be compared with (%V bur ) of 35.5% isoelectronic sterically-unbiased ligand (A4), which may indicate that the presence of the amino substituent in the C5 position leads to a significant increase of steric volume (cf.16 of 42.8%, Δ of 7.3%) This steric increase effect can be compared with steric impact from 1,3-Bis(2,4,6- trimethylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IMes): %Vbur = 36.5% to 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene (IPr): %V bur = 45.4% (Δ of 8.9%). Furthermore, there is a significant variation of steric impact within the series of NHC ligands disclosed herein which is enforced by the N-wingtip substituent (40.9% to 47.8%, Δ of 6.9%). Without wishing to be bound by theory, these values indicate that this class of ligands (1) is characterized by the steric effect in the range of imidazolylidene IMes/IPr, which has been determined as ideal for catalysis, and (2) enables the variation of the size of catalytic pocket, which is an important factor in tuning reactivity to a specific class of substrates and reactions. Furthermore, there is coplanarity of the hard N atom and transition-metals coordinated to the NHC center (e.g. [16, Me2N–Au distance of 3.126 Å; [18, Me2N–Au of 3.144 Å; [22, PipN–Au of 3.114 Å), which is unavailable in other classes of NHC ligands developed to date. Example 10: Catalysis Catalytic studies were performed to evaluate the catalytic activity of certain compounds of the present disclosure. Four non-limiting classes of reactions have been developed, including: (1) Oxidative Au(I)/Au(III) C–C coupling by C–H arylation (FIG.4); (2) Oxidative Au(I)/Au(III) C–C coupling by C–H heteroarylation (FIG.5); (3) Oxidative Au(I)/Au(III) C–N coupling by C–X amination (FIG.6); and (4) Electrophilic Au(I) hydroamination of internal alkynes with aliphatic and aromatic amines (FIG.7). Feasibility studies (Au catalysis) have been conducted demonstrating the following reactions: (1) Electrophilic Au(I) hydroamination of internal alkynes with parent hydrazine; (2) Electrophilic Au(I) hydroamination of terminal alkynes with aromatic amines; (3) Electrophilic Au(I) hydration of internal alkynes. Feasibility studies (Pd(0)/Pd(II) catalysis) have been conducted demonstrating the following reactions: (1) amination of Ar–Cl; (2) Kumada cross- coupling of Ar–Cl; (3) arylation of ArC(O)–Cl; and (4) aminocarbonylation of Ar–I. The feasibility studies represent unoptimized results for the use of the compounds of the present disclosure in Au and Pd-catalysis. Nonetheless, the utility of the compounds disclosed herein has been demonstrated in a number of catalytic transformations. General Procedure for Oxidative Au(I)/Au(III) C–C Coupling by C–H Arylation (General Procedure I) An oven-dried vial equipped with a stir bar was charged with iodoarene (1.0 equiv), arene (1.0 equiv), [Au(NHC)X] (5 mol%), AgNTf2 (1.1 equiv), MeOH (0.125 M) at room temperature. The reaction mixture was placed in a preheated oil bath at 80 °C, and stirred for 16 hours at 80 °C. After the indicated time, the reaction mixture was cooled down to room temperature, diluted with CH2Cl2 (10 mL), filtered, and concentrated. The residue was analyzed by 1 H NMR (CDCl3, 500 MHz) and GC-MS using internal standard. Purification by chromatograpFThy on silica gel (EtOAc/hexanes or CH 2 Cl 2 /MeOH) afforded the title product. X, R ’ , and R ’’ are defined within the scope of the present disclosure. S ' ' ' ' According to General Procedure (I), the reaction of methyl 4-iodobenzoate (0.2 mmol, 1.0 equiv), 1,3,5-trimethoxybenzene (0.20 mmol, 1.0 equiv), 16 (0.01 mmol, 5 mol%), AgNTf2 (0.22 mmol, 1.1 equiv), MeOH (0.125 M) for 16 hours at 80 °C, afforded the title product in 99% yield (60.0 mg). 1 H NMR (500 MHz, CDCl3) δ 8.06 (d, J = 8.3 Hz, 2H), 7.43 (d, J = 8.3 Hz, 2H), 6.24 (s, 2H), 3.93 (s, 3H), 3.88 (s, 3H), 3.73 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 167.30, 161.04, 158.24, 139.46, 131.37, 128.88, 128.02, 111.42, 90.91, 55.86, 55.42, 51.98. Spectroscopic data matched literature values. General Procedure for Oxidative Au(I)/Au(III) C–C Coupling by C–H Heteroarylation (General Procedure II) An oven-dried vial equipped with a stir bar was charged with iodoarene (1.0 equiv), heteroarene (2.0 equiv), [Au(NHC)Cl] (5 mol%), AgNTf2 (1.1 equiv), MeOH (0.125 M) at room temperature. The reaction mixture was placed in a preheated oil bath at 80 °C, and stirred for 16 hours at 80 °C. After the indicated time, the reaction mixture was cooled down to room temperature, diluted with CH2Cl2 (10 mL), filtered, and concentrated. The residue was analyzed by 1 H NMR (CDCl 3 , 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded the title product. Note: “Het” indicates a heteroaryl compound and/or moiety, and is not limited to 6-membered heteroaryl species. X, R ’ , and R ’’ are defined within the scope of the present disclosure. Synthesis of 1,3-diphenyl-1H-indole According to General Procedure II, the reaction of iodobenzene (0.2 mmol, 1.0 equiv), 1- phenyl-1H-indole (0.40 mmol, 2.0 equiv), 16 (0.01 mmol, 5 mol%), AgNTf2 (0.22 mmol, 1.1 equiv), MeOH (0.125 M) for 16 hours at 80 °C, afforded the title product in 94% yield (50.6 mg). 1 H NMR (500 MHz, CDCl3) δ 8.02 – 7.98 (m, 1H), 7.75 – 7.70 (m, 2H), 7.61 (d, J = 7.7 Hz, 1H), 7.54 (dt, J = 14.0, 6.8 Hz, 5H), 7.48 (t, J = 7.7 Hz, 2H), 7.41 – 7.36 (m, 1H), 7.32 (t, J = 7.4 Hz, 1H), 7.30 – 7.24 (m, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 139.56, 136.69, 135.14, 129.72, 128.86, 127.64, 127.17, 126.70, 126.25, 125.56, 124.52, 122.83, 120.91, 120.17, 119.15, 110.86. Spectroscopic data matched literature values. General Procedure for Oxidative Au(I)/Au(III) C–N Coupling by C–X Amination (General Procedure III) An oven-dried vial equipped with a stir bar was charged with iodoarene (1.0 equiv), aniline (1.0 equiv), [Au(NHC)Cl] (2.5-5 mol%), AgNTf2 (1.1 equiv), MeOH (0.125 M) at room temperature. The reaction mixture was placed in a preheated oil bath at 80 °C, and stirred for 16 hours at 80 °C. After the indicated time, the reaction mixture was cooled down to room temperature, diluted with CH2Cl2 (10 mL), filtered, and concentrated. The residue was analyzed by 1 H NMR (CDCl3, 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes or CH 2 Cl 2 /MeOH) afforded the title product. X, R ’ and R ’’ are defined within the scope of the present disclosure. S According to General Procedure III, the reaction of 1-iodo-4-nitrobenzene (0.2 mmol, 1.0 equiv), aniline (0.20 mmol, 1.0 equiv), 19 (0.005 mmol, 2.5 mol%), AgNTf 2 (0.22 mmol, 1.1 equiv), MeOH (0.125 M) for 16 hours at 80 °C, afforded the title product in 99% yield (42.4 mg). 1 H NMR (500 MHz, CDCl3) δ 8.15 – 8.07 (m, 2H), 7.39 (t, J = 7.9 Hz, 2H), 7.21 (d, J = 7.6 Hz, 2H), 7.17 (t, J = 7.4 Hz, 1H), 6.97 – 6.82 (m, 2H), 6.28 (s, 1H). 13 C NMR (126 MHz, CDCl 3 ) δ 150.17, 139.83, 139.50, 129.77, 126.26, 124.71, 121.96, 113.71. Spectroscopic data matched literature values. General Procedure for Electrophilic Au(I) Hydroamination of Internal Alkynes with Aliphatic and Aromatic Amines (General Procedure IV) An oven-dried vial equipped with a stir bar was charged with alkyne (1.0 equiv), amine (1.2 equiv), [Au(NHC)Cl] (2.5 mol%), NaBAr F (5.0 mol%), toluene (0.5 M) under argon at room temperature. The reaction mixture was placed in a preheated oil bath at 110 °C and stirred for 16 hours. After the indicated time, the reaction mixture was cooled down to room temperature and concentrated. Sodium triacetoxyborohydride (2.0 equiv), acetic acid (2.0 equiv) and CH 2 Cl 2 (0.1 M) were added and the reaction mixture was stirred for 24 h at room temperature. After the indicated time, the reaction was quenched with NaOH (1.0 M, aq) and extracted with CH 2 Cl 2 (15 ml). The combined organic phases were dried, filtered and concentrated. The residue was analyzed by 1 H NMR (CDCl 3 , 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded the title product. R I , R II , X, R ’ , and R ’’ are defined within the scope of the present disclosure. Synthesis of 1-(1,2-diphenylethyl)piperidine According to the general procedure, the reaction of diphenylacetylene (0.2 mmol, 1.0 equiv), piperidine (0.24 mmol, 1.2 equiv), 22 (0.005 mmol, 2.5 mol%), NaBAr F (0.01 mmol, 5.0 mol%), toluene (0.5 M) at 110 °C and stirred for 16 hours, afforded after reduction with sodium triacetoxyborohydride (0.4 mmol, 2.0 equiv), acetic acid (0.4 mmol, 2.0 equiv) in CH2Cl2 (0.1 M), the title product in 99% yield (52.0 mg). 1 H NMR (500 MHz, CDCl3) δ 7.24 (d, J = 7.3 Hz, 2H), 7.20 (t, J = 7.1 Hz, 1H), 7.13 (t, J = 7.8 Hz, 4H), 7.08 (t, J = 7.2 Hz, 1H), 7.02 – 6.97 (m, 2H), 3.69 – 3.54 (m, 1H), 3.40 – 3.26 (m, 1H), 3.02 (dd, J = 13.3, 9.4 Hz, 1H), 2.45 (s, 4H), 1.58 (s, 4H), 1.37 (p, J = 6.1 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 139.91, 139.30, 129.39, 128.98, 127.88, 127.72, 126.92, 125.68, 72.38, 51.42, 39.12, 26.29, 24.61. Spectroscopic data matched literature values. General Procedure for Electrophilic Au(I) Hydroamination of Internal Alkynes with An oven-dried vial equipped with a stir bar was charged with alkyne (1.0 equiv), hydrazine monohydrate (1.2 equiv), [Au(NHC)Cl] catalyst (5 mol%), NaBAr F (5 mol%), toluene (0.5 M) under argon at room temperature. The reaction mixture was placed in a preheated oil bath at 90 °C and stirred for 16 hours. After the indicated time, the reaction mixture was cooled down to room temperature and concentrated. The residue was analyzed by 1 H NMR (CDCl3, 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded (1,2-diphenylethylidene)hydrazine. Catalysts: 22 (81% yield); 18 (78% yield); IPr-AuCl (80% yield). 1 H NMR (500 MHz, CDCl3) δ 7.73 (d, J = 7.3 Hz, 2H), 7.42 – 7.31 (m, 6H), 7.27 (s, 2H), 5.42 (s, 2H), 4.09 (s, 2H). 13 C NMR (126 MHz, CDCl3) δ 148.70, 139.14, 135.36, 129.13, 128.46, 128.19, 127.98, 126.90, 125.64, 32.45. Spectroscopic data matched literature values. R ’ and R ’’ are defined within the scope of the present disclosure. General Procedure for Electrophilic Au(I) Hydroamination of Terminal alkynes with Aromatic Amines (General Procedure VI) An oven-dried vial equipped with a stir bar was charged with alkyne (1.2 equiv), aniline (1.0 equiv), [Au(NHC)Cl] catalyst (0.1 mol%), NaBAr F (0.2 mol%), toluene (1.5 M) under argon at room temperature. The reaction mixture was placed in a preheated oil bath at 80 °C and stirred for 16 hours. After the indicated time, the reaction mixture was cooled down to room temperature and concentrated. The residue was analyzed by 1 H NMR (CDCl 3 , 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded N,1-diphenylethan-1-imine. Catalysts: 16 (89% yield); 22 (90% yield); 19 (83% yield); IPr-AuCl (83% yield). 1 H NMR (500 MHz, CDCl 3 ) δ 8.04 – 7.95 (m, 2H), 7.46 (d, J = 7.1 Hz, 3H), 7.36 (t, J = 7.8 Hz, 2H), 7.09 (t, J = 7.4 Hz, 1H), 6.87 – 6.78 (m, 2H), 2.24 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 165.54, 151.68, 139.49, 130.50, 128.97, 128.39, 127.20, 123.25, 119.41, 17.41. Spectroscopic data matched literature values. R ’ and R ’’ are defined within the scope of the present disclosure. General Procedure for Electrophilic Au(I) Hydration of Internal Alkynes (General Procedure VII) An oven-dried vial equipped with a stir bar was charged with alkyne (1.0 equiv), [Au(NHC)Cl] catalyst (0.1 mol%), AgSbF6 (0.2 mol%), dioxane/H2O = 2/1 (1.0 M) at room temperature. The reaction mixture was placed in a preheated oil bath at 120 °C and stirred for 18 hours. After the indicated time, the reaction mixture was cooled down to room temperature and concentrated. The residue was analyzed by 1 H NMR (CDCl3, 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded 1,2- diphenylethan-1-one. Catalysts: 19 (98% yield); IPr-AuCl (77% yield). 1 H NMR (500 MHz, CDCl 3 ) δ 8.14 – 8.00 (m, 2H), 7.63 – 7.55 (m, 1H), 7.55 – 7.44 (m, 2H), 7.42 – 7.23 (m, 5H), 4.31 (s, 2H). Spectroscopic data matched literature values. R ’ and R ’’ are defined within the scope of the present disclosure. General Procedure for Pd-Catalyzed Amination of Aryl Chlorides (General Procedure VIII) An oven-dried vial equipped with a stir bar was charged with aryl chloride (1.0 equiv), amine (2.0 equiv), [Pd-NHC] catalyst (3 mol%), dioxane (0.25 M) under argon at room temperature. LiHMDS (3.0 equiv, 1.0 M in THF) was added, the reaction mixture was placed in a preheated oil bath at 80 °C and stirred for 16 hours at 80 °C. After the indicated time, the reaction mixture was cooled down to room temperature and extracted with EtOAc. The combined organic layers were dried, filtered and concentrated. The residue was analyzed by 1 H NMR (CDCl3, 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded 4-(4-methoxyphenyl)morpholine. Catalysts: 26 (99% yield); 32 (99% yield); IPrCinPdCl (99% yield); [(cinnamyl)PdCl] 2 (0% yield). 1 H NMR (500 MHz, CDCl 3 ) δ 6.88 (q, J = 8.9 Hz, 4H), 3.90 – 3.83 (m, 4H), 3.77 (s, 3H), 3.11 – 3.02 (m, 4H). 13 C NMR (126 MHz, CDCl3) δ 154.02, 145.65, 117.85, 114.53, 67.05, 55.59, 50.86. Spectroscopic data matched literature values. General Procedure for Pd-Catalyzed Kumada Cross-Coupling of Aryl Chlorides (General Procedure IX) An oven-dried vial equipped with a stir bar was charged with aryl chloride (1.0 equiv), [Pd-NHC] catalyst (3 mol%), dioxane (0.25 M) under argon at room temperature. PhMgBr (2.0 equiv, 1.0 M in THF) was added, the reaction mixture was placed in a preheated oil bath at 80 °C and stirred for 16 hours at 80 °C. After the indicated time, the reaction mixture was cooled down to room temperature and extracted by EtOAc. The combined organic layers were dried, filtered and concentrated. The residue was analyzed by 1 H NMR (CDCl 3 , 500 MHz) and GC-MS using internal standard Purification by chromatography on silica gel (EtOAc/hexanes) afforded 4- methoxy-1,1'-biphenyl.26 (99% yield); 32 (99% yield); 33 (99% yield); IPrCinPdCl (99% yield); [(Cinnamyl)PdCl]2 (0% yield). 1 H NMR (500 MHz, CDCl3) δ 7.55 (dd, J = 10.7, 8.1 Hz, 4H), 7.42 (t, J = 7.7 Hz, 2H), 7.31 (t, J = 7.4 Hz, 1H), 6.99 (d, J = 8.7 Hz, 2H), 3.86 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 159.17, 140.86, 133.81, 128.73, 128.17, 126.76, 126.67, 114.23, 55.37. Spectroscopic data matched literature values. R ’ and R ’’ are defined within the scope of the present disclosure. General Procedure for Pd-Catalyzed Arylation of Aroyl Chlorides (General Procedure X) An oven-dried vial equipped with a stir bar was charged with aroyl chloride (1.0 equiv), boronic acid (2.0 equiv), K 2 CO 3 (3.0 equiv), [Pd-NHC] catalyst (3 mol%), dioxane (0.25 M) under argon at room temperature. The reaction mixture was placed in a preheated oil bath at 130 °C and stirred for 16 hours at 130 °C. After the indicated time, the reaction mixture was cooled down to room temperature, diluted with CH 2 Cl 2 , filtered and concentrated. The residue was analyzed by 1 H NMR (CDCl3, 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded (4-methoxyphenyl)(p-tolyl)methanone. 26 (70% yield); IPrCinPdCl (72% yield); [(Cinnamyl)PdCl] 2 (25% yield). 1 H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 8.8 Hz, 2H), 7.72 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 3.91 (s, 3H), 2.47 (s, 3H). Spectroscopic data matched literature values. R ’ and R ’’ are defined within the scope of the present disclosure. General Procedure for Pd-Catalyzed Aminocarbonylation of Aryl Iodides (General Procedure XI) An oven-dried vial equipped with a stir bar was charged with aryl iodide (1.0 equiv), amine (1.2 equiv), K3PO4 (3.0 equiv), [Pd-NHC] catalyst (3 mol%), toluene (0.25 M) at room temperature. The vial was charged with CO gas (1 atm), placed in a preheated oil bath at 90 °C and stirred for 16 hours at 90 °C. After the indicated time, the reaction mixture was cooled down to room temperature, diluted with CH2Cl2, filtered and concentrated. The residue was analyzed by 1 H NMR (CDCl 3 , 500 MHz) and GC-MS using internal standard. Purification by chromatography on silica gel (EtOAc/hexanes) afforded N-Phenyl-1-naphthamide.26 (99% yield); IPrCinPdCl (96% yield); [(Cinnamyl)PdCl]2 (0% yield). 1 H NMR (500 MHz, CDCl3) δ 8.37 (d, J = 7.9 Hz, 1H), 7.97 (d, J = 8.3 Hz, 1H), 7.91 (d, J = 7.1 Hz, 1H), 7.72 (dd, J = 20.8, 6.8 Hz, 4H), 7.60 – 7.54 (m, 2H), 7.52 – 7.48 (m, 1H), 7.40 (t, J = 7.1 Hz, 2H), 7.19 (t, J = 7.1 Hz, 1H). 13 C NMR (126 MHz, CDCl3) δ 167.55, 138.05, 133.79, 131.09, 129.20, 128.46, 127.41, 126.64, 125.28, 125.10, 124.78, 124.71, 119.97. Spectroscopic data matched literature values. R ’ and R ’’ are defined within the scope of the present disclosure. The terms and expressions employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present application. Thus, it should be understood that although the present application describes specific embodiments and optional features, modification and variation of the compositions, methods, and concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present application. Enumerated Embodiments The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance: Embodiment 1 provides a compound of formula (I) selected from the group consisting of: w T 1 is N or CR a1 ; T 2 is N or CR a2 ; T 3 is N or CR a3 ; X is a counter anion; Y 1 , if present, is selected from the group consisting of OR b1 and N(R b1 )(R b2 ); Y 2 , if present, is selected from the group consisting of N(R b1 )(R b2 ) and optionally substituted phenyl; Z is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 8 heteroaryl, wherein each optional substituent in Z is independently at least one selected from the group consisting of H, halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, NO 2 , OR A , N(R A )(R B ), C(=O)R A , C(=O)N(R A )(R B ), C(=O)OR B , N(R A )S(=O) 2 R B , S(=O) 2 N(R A ), optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein the C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 12 heterocyclyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl are each optionally substituted with at least one substituent selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl; R a1 , R a2 , R a3 , R a5 , and R a6 , if present, are each independently selected from the group consisting of H, halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, NO 2 , OR A , N(R A )(R B ), C(=O)R A , C(=O)N(R A )(R B ), C(=O)OR B , N(R A )S(=O)2R B , S(=O)2N(R A ), optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 8 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of R a1 , R a2 , R a3 , R a5 , and R a6 is independently selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of R a1 , R a2 , R a3 , R a5 , and R a6 may combine with the carbon atoms to which they are bound to form an optionally substituted C 5 -C 12 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, or optionally substituted C 6 -C 10 aryl; R a4 is selected from the group consisting of H, C 1 -C 6 alkyl, C 6 -C 10 aryl, and C 2 -C 12 heterocyclyl; R b1 and R b2 are each independently selected from the group consisting of H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 8 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein R b1 and R b2 may combine with the atom to which they are bound to form an optionally substituted C 2 -C 12 heterocyclyl, wherein each optional substituent in each of R b1 and R b2 is independently selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl; and R A and R B are each independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 3 haloalkyl, C 2 -C 6 alkenyl, benzyl, naphthyl, C4-C 10 heteroaryl, and phenyl, wherein each substituent in R A and R B is optionally substituted with at least one substituent selected from the group consisting of CN, NO 2 , C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, and halogen. Embodiment 2 provides the compound of Embodiment 1, wherein at least one of the following occurs: (a) T 1 is CR a1 ; (b) T 2 is CR a2 ; and (c) T 3 is CR a3 . Embodiment 3 provides the compound of Embodiment 1 or 2, wherein Z is: , wherein: R c1 , R c2 , R c3 , R c4 , and R c5 are each independently selected from the group consisting of H, halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, NO 2 , OR A , N(R A )(R B ), C(=O)R A , C(=O)N(R A )(R B ), C(=O)OR B , N(R A )S(=O) 2 R B , S(=O) 2 N(R A ), optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of R c1 , R c2 , R c3 , R c4 , and R c5 is independently selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of R c1 , R c2 , R c3 , R c4 , and R c5 may combine with the carbon atoms to which they are bound to form an optionally substituted C 5 -C 12 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, or optionally substituted C 6 -C 10 aryl. Embodiment 4 provides the compound of any one of Embodiments 1-3, wherein at least one of the following occurs: (a) at least one of R a1 , R a2 , and R a3 is H; (b) at least two of R a1 , R a2 , and R a3 are H; and (c) each of R a1 , R a2 , and R a3 are H. Embodiment 5 provides the compound of any one of Embodiments 1-4, wherein X is selected from the group consisting of H, OS(=O)2R A , OC(=O)R A , N(C(=O)R A )2, halogen, tetracoordinate boronate, hexacoordinate phosphorus, optionally substituted C 6 -C 10 aryl, and optionally substituted C 2 -C 10 heteroaryl, wherein each optional substituent in the C 6 -C 10 aryl and C 2 -C 8 heteroaryl is independently selected from the group consisting of a halogen, CN, NO2, C 1 - C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 3 -C 8 cycloalkyl, phenyl, and C 2 -C 8 heterocyclyl Embodiment 6 provides the compound of Embodiment 5, wherein X is Cl. Embodiment 7 provides the compound of any one of Embodiments 1-6, wherein one of the following applies: (a) R b1 and R b2 are each independently selected from the group consisting of H, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, and i-butyl; or (b) R b1 and R b2 combine with the nitrogen atom to which they are bound to form a morpholinyl, piperidinyl, fluorenyl, or optionally substituted pyrazolyl. Embodiment 8 provides the compound of any one of Embodiments 1-7, wherein Y 1 is selected from the group consisting of OMe, NMe2, and NEt2. Embodiment 9 provides the compound of any one of Embodiments 1-7, wherein Y 1 is selected from the group consisting o Embodiment 10 provides the compound of any one of Embodiments 1-7, wherein Y 2 is selected from the group consisting of NMe2, NEt2, Embodiment 11 provides the compound of any one of Embodiments 3-10, wherein R c1 and R c5 are each independently selected from the group consisting of methyl, i-propyl, and diphenylmethyl. Embodiment 12 provides the compound of Embodiment 11, wherein R c1 and R c5 are identical. Embodiment 13 provides the compound of any one of Embodiments 3-12, wherein R c3 is selected from the group consisting of H and methyl. Embodiment 14 provides the compound of any one of Embodiments 3-13, wherein R c2 and R c4 are each H. Embodiment 15 provides the compound of any one of Embodiments 1-14, wherein Z is selected from the group consisting o Embodiment 16 provides the compound of any one of Embodiments 1-15, which is selected from the group consisting of: 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-2-ium chloride; 5-(dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(dimethylamino)imidazo [1,5-a]pyridin-2-ium chloride; 5-(diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyri din-2-ium chloride; 5-(diethylamino)-2-mesitylimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(diethylamino)imidazo[ 1,5-a]pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]py ridin-2-ium chloride; 2-mesityl-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(piperidin-1-yl)imidaz o[1,5-a]pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-morpholinoimidazo[1,5-a]pyridin- 2-ium chloride; 2-mesityl-5-morpholinoimidazo[1,5-a]pyridin-2-ium chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-morpholinoimidazo[1,5- a]pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-(3,5-diphenyl-1H-pyrazol-1-yl)im idazo[1,5-a]pyridin-2-ium chloride; 5-(9H-carbazol-9-yl)-2-(2,6-diisopropylphenyl)imidazo[1,5-a] pyridin-2-ium chloride; 2-(2,6-diisopropylphenyl)-5-methoxyimidazo[1,5-a]pyridin-2-i um chloride; 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-2-ium chloride; 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quin olin-2-ium chloride; 2-(2,6-Diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]qu inolin-2-ium chloride; 2-(2,6-Diisopropylphenyl)-9-morpholinoimidazo[1,5-a]quinolin -2-ium chloride; 9-(Dimethylamino)-2-mesitylimidazo[1,5-a]quinolin-2-ium chloride; and 2-(2,6-Diisopropylphenyl)-9-(2,4,6-trimethylphenyl)imidazo[1 ,5-a]quinolin-2-ium chloride. Embodiment 17 provides a method of preparing the compound of formula (Ia) of any one of Embodiments 1-9 and 11-16, the method comprising: contacting a compound of formula (A): a compound of formula (B): paraformaldehyde: , in the presence of an acid to form the compound of formula (Ia). Embodiment 18 provides the method of Embodiment 17, wherein the contacting occurs in the presence of a solvent, wherein the solvent is optionally ethanol. Embodiment 19 provides the method of Embodiment 17 or 18, wherein the contacting occurs at a temperature ranging from about 40 °C to about 80 °C. Embodiment 20 provides the method of any one of Embodiments 17-19, wherein the contacting for a period of time ranging from about 12 to about 36 h. Embodiment 21 provides a compound of formula (II) selected from the group consisting of: wherein: M is a transition metal; L is a ligand of M, wherein each occurrence of L can be the same or different; each occurrence of is a single or double bond, wherein no more than one bonding a C atom and a N atom is a double bond; T 1 is N or CR a1 ; T 2 is N or CR a2 ; T 3 is N or CR a3 ; X is a counter anion; Y 1 , if present, is selected from the group consisting of OR b1 and N(R b1 )(R b2 ); Y 2 , if present, is selected from the group consisting of N(R b1 )(R b2 ) and optionally substituted phenyl; Z is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 8 heteroaryl, wherein each optional substituent in Z is independently at least one selected from the group consisting of H, halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, NO2, OR A , N(R A )(R B ), C(=O)R A , C(=O)N(R A )(R B ), C(=O)OR B , N(R A )S(=O)2R B , S(=O)2N(R A ), optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein the C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 12 heterocyclyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl are each optionally substituted with at least one substituent selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl; R a1 , R a2 , R a3 , R a5 , and R a6 , if present, are each independently selected from the group consisting of H, halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, NO2, OR A , N(R A )(R B ), C(=O)R A , C(=O)N(R A )(R B ), C(=O)OR B , N(R A )S(=O) 2 R B , S(=O) 2 N(R A ), optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 8 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of R a1 , R a2 , R a3 , R a5 , and R a6 is independently selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of R a1 , R a2 , R a3 , R a5 , and R a6 may combine with the carbon atoms to which they are bound to form an optionally substituted C5-C 12 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, or optionally substituted C 6 -C 10 aryl; R a4 is selected from the group consisting of H, C 1 -C 6 alkyl, C 6 -C 10 aryl, and C 2 -C 12 heterocyclyl; R b1 and R b2 are each independently selected from the group consisting of H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 8 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein R b1 and R b2 may combine with the atom to which they are bound to form an optionally substituted C 2 -C 12 heterocyclyl, wherein each optional substituent in each of R b1 and R b2 is independently selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl; R A and R B are each independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 3 haloalkyl, C 2 -C 6 alkenyl, benzyl, naphthyl, C 4 -C 10 heteroaryl, and phenyl, wherein each substituent in R A and R B is optionally substituted with at least one substituent selected from the group consisting of CN, NO 2 , C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, and halogen; and n is an integer which is selected from the group consisting of 0, 1, 2, and 3. Embodiment 22 provides the compound of Embodiment 21, wherein at least one of the following occurs: (a) T 1 is CR a1 ; (b) T 2 is CR a2 ; and (c) T 3 is CR a3 . Embodiment 23 provides the compound of Embodiment 21 or 22, wherein Z is: , wherein: R c1 , R c2 , R c3 , R c4 , and R c5 are each independently selected from the group consisting of H, halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, CN, NO2, OR A , N(R A )(R B ), C(=O)R A , C(=O)N(R A )(R B ), C(=O)OR B , N(R A )S(=O)2R B , S(=O)2N(R A ), optionally substituted C 1 -C 6 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, optionally substituted C 2 -C 6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, wherein each optional substituent in each of R c1 , R c2 , R c3 , R c4 , and R c5 is independently selected from the group consisting of halogen, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, benzyl, phenyl, and naphthyl, and C 2 -C 12 heterocyclyl, wherein two vicinal substituents selected from the group consisting of R c1 , R c2 , R c3 , R c4 , and R c5 may combine with the carbon atoms to which they are bound to form an optionally substituted C5-C 12 cycloalkyl, optionally substituted C 2 -C 12 heterocyclyl, or optionally substituted C 6 -C 10 aryl. Embodiment 24 provides the compound of any one of Embodiments 21-23, wherein M is selected from the group consisting of Cu, Ag, Au, Pd, Ni, Pt, Co, Rh, Ir, Fe, Ru, and Os. Embodiment 25 provides the compound of Embodiment 24, wherein M is selected from the group consisting of Au, Pd, Rh, Ag and Cu. Embodiment 26 provides the compound of any one of Embodiments 21-25, wherein X is selected from the group consisting of H, OS(=O)2R A , OC(=O)R A , N(C(=O)R A )2, halogen, tetracoordinate boronate, hexacoordinate phosphorus, optionally substituted C 6 -C 10 aryl, and optionally substituted C 2 -C 10 heteroaryl, wherein each optional substituent in the C 6 -C 10 aryl and C 2 -C 8 heteroaryl is independently selected from the group consisting of a halogen, CN, NO2, C 1 - C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 3 -C 8 cycloalkyl, phenyl, and C 2 -C 8 heterocyclyl. Embodiment 27 provides the compound of Embodiment 26, wherein X is selected from the group consisting of Cl, trifluoromethanesulfonate (OTf), bis(trifluoromethansulfonyl)amide (NTf 2 ), and allylbenzene anion (i.e., 3-phenylpropen-3-ide and/or 1-phenylpropen-3-ide). Embodiment 28 provides the compound of any one of Embodiments 21-27, wherein L is selected from the group consisting of Y 1 , Y 2 , carbon monoxide (CO), optionally substituted C 2 - C 12 alkene, and optionally substituted C 5 -C 12 cycloalkene, wherein each optional substituent in the C 2 -C 12 alkene and C 5 -C 12 cycloalkene is independently selected from the group consisting of a halogen, CN, NO2, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkyl, C 3 -C 8 cycloalkyl, phenyl, and C 2 -C 8 heterocyclyl. Embodiment 29 provides the compound of any one of Embodiments 21-27, wherein L is selected from the group consisting of cyclooctadiene (COD) and carbon monoxide (CO). Embodiment 30 provides the compound of any one of Embodiments 21-29, wherein at least one of the following occurs: (a) at least one of R a1 , R a2 , and R a3 is H; (b) at least two of R a1 , R a2 , and R a3 are H; and (c) each of R a1 , R a2 , and R a3 are H. Embodiment 31 provides the compound of any one of Embodiments 21-30, wherein one of the following applies: (a) R b1 and R b2 , if present, are each independently selected from the group consisting of H, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, and i-butyl; or (b) R b1 and R b2 combine with the nitrogen atom to which they are bound to form a morpholinyl or piperidinyl. Embodiment 32 provides the compound of any one of Embodiments 21-31, wherein Y 1 is selected from the group consisting of OMe, NMe2, and NEt2. Embodiment 33 provides the compound of any one of Embodiments 21-31, wherein Y 1 is selected from the group consisting o Embodiment 34 provides the compound of any one of Embodiments 21-31, wherein Y 2 is selected from the group consisting of NMe 2 , NEt 2 , , , . Embodiment 35 provides the compound of any one of Embodiments 23-34, wherein R c1 and R c5 are each independently selected from the group consisting of methyl, i-propyl, and diphenylmethyl. Embodiment 36 provides the compound of any one of Embodiments 23-35, wherein R c1 and R c5 are identical. Embodiment 37 provides the compound of any one of Embodiments 23-36, wherein R c3 is selected from the group consisting of H and methyl. Embodiment 38 provides the compound of any one of Embodiments 23-37, wherein R c2 and R c4 are each H. Embodiment 39 provides the compound of any one of Embodiments 21-38, wherein Z is s Embodiment 40 provides the compound of any one of Embodiments 21-39, which is selected from the group consisting of: 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene gold(I) chloride; 5-(dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(dimethylamino)imidazo [1,5-a]pyridin-3-ylidene gold(I) chloride; 5-(diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1,5-a]pyri din-3-ylidene gold(I) chloride; 5-(diethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(diethylamino)imidazo[ 1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-diisopropylphenyl)-5-(piperidin-1-yl)imidazo[1,5-a]py ridin-3-ylidene gold(I) chloride; 2-mesityl-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-dibenzhydryl-4-methylphenyl)-5-(piperidin-1-yl)imidaz o[1,5-a]pyridin-3-ylidene gold(I) chloride; 2-(2,6-diisopropylphenyl)-5-methoxyimidazo[1,5-a]pyridin-3-y lidene gold(I) chloride; cinnamyl[2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[ 1,5-a]pyridine-3- ylidene]chloropalladium(II); cinnamyl[5-(dimethylamino)-2-mesitylimidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[2-(2,6-dibenzhydryl-4-methylphenyl)-5-(dimethylamin o)imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[5-(diethylamino)-2-(2,6-diisopropylphenyl)imidazo[1 ,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[5-(diethylamino)-2-mesitylimidazo[1,5-a]pyridin-3-y lidene]chloropalladium(II); cinnamyl[2-(2,6-dibenzhydryl-4-methylphenyl)-5-(diethylamino )imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[2-(2,6-diisopropylphenyl)-5-(piperidin-1-yl)imidazo [1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[2-mesityl-5-(piperidin-1-yl)imidazo[1,5-a]pyridin-3 -ylidene]chloropalladium(II); cinnamyl[2-(2,6-dibenzhydryl-4-methylphenyl)-5-(piperidin-1- yl)imidazo[1,5-a]pyridin-3- ylidene]chloropalladium(II); cinnamyl[2-(2,6-diisopropylphenyl)-5-morpholinoimidazo[1,5-a ]pyridin-3- ylidene]chloropalladium(II); 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene silver(I) chloride; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene copper(I) chloride; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3- ylidene(cyclooctadiene)rhodium(I) chloride; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3- ylidene(cyclooctadiene)rhodium(I) triflate; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3- ylidene(bis(carbonyl))rhodium(I) triflate; 2-(2,6-diisopropylphenyl)-5-(dimethylamino)imidazo[1,5-a]pyr idin-3-ylidene gold(I) bis(trifluoromethanesulfonyl)amide; 2-(2,6-diisopropylphenyl)-5-(morpholin-4-yl)imidazo[1,5-a]py ridin-3-ylidene gold(I) chloride; 2-(2,4,6-trimethylphenyl)-5-(morpholin-4-yl)imidazo[1,5-a]py ridin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quin olin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]qu inolin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(morpholin -4-yl)imidazo[1,5-a]quinolin-3-ylidene silver(I) chloride; 2-(2,4,6-trimethylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene silver(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(diethylamino)imidazo[1,5-a]quin olin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(piperidin-1-yl)imidazo[1,5-a]qu inolin-3-ylidene gold(I) chloride; 2-(2,6-Diisopropylphenyl)-9-(morpholin -4-yl)imidazo[1,5-a]quinolin-3-ylidene gold(I) chloride; 2-(2,4,6-trimethylphenyl)-9-(dimethylamino)imidazo[1,5-a]qui nolin-3-ylidene gold(I) chloride; and 2-(2,6-Diisopropylphenyl)-9-(2,4,6-trimethylphenyl)imidazo[1 ,5-a]quinolin-3-ylidene gold(I) chloride. Embodiment 41 provides a method of promoting a reaction between a first reagent and an aryl iodide, the method comprising contacting the first reagent and the aryl iodide in the presence of the compound of any one of Embodiments 21-40 and optionally in the presence of a Lewis acid. Embodiment 42 provides the method of Embodiment 41, wherein M is Au in the compound of any one of Embodiments 20-38. Embodiment 43 provides the method of Embodiment 41 or 42, wherein the compound of any one of Embodiments 20-38 is present in an amount ranging from about 0.1 to about 10 mol%. Embodiment 44 provides the method of any one of Embodiments 41-43, wherein the first reagent is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 45 provides the method of any one of Embodiments 41-44, wherein the aryl iodide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH2, C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . Embodiment 46 provides the method of any one of Embodiments 41-45, wherein the Lewis acid is AgNTf2. Embodiment 47 provides the method of any one of Embodiments 41-46, wherein the contacting occurs in the presence of a solvent, wherein the solvent is optionally MeOH. Embodiment 48 provides the method of any one of Embodiments 41-47, wherein the contacting occurs at a temperature ranging from about 40 °C to about 80 °C. Embodiment 49 provides the method of any one of Embodiments 41-48, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. Embodiment 50 provides a method of promoting a reaction between an aniline and an aryl iodide, the method comprising contacting the aniline and the aryl iodide in the presence of the compound of any one of Embodiments 21-40 and optionally in the presence of a Lewis acid. Embodiment 51 provides the method of Embodiment 50, wherein M is Au in the compound of any one of Embodiments 21-40. Embodiment 52 provides the method of Embodiment 50 or 51, wherein the compound of any one of Embodiments 20-38 is present in an amount ranging from about 0.1 to about 10 mol%. Embodiment 53 provides the method of any one of Embodiments 50-52, wherein the aniline is selected from the group consisting of optionally substituted C 6 -C 10 aryl and C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one NH2, and wherein each optional substituent is at least one selected from the group consisting of of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH2, C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 54 provides the method of any one of Embodiments 50-53, wherein the aryl iodide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . Embodiment 55 provides the method of any one of Embodiments 50-54, wherein the Lewis acid is AgNTf2. Embodiment 56 provides the method of any one of Embodiments 50-55, wherein the contacting occurs in the presence of a solvent, wherein the solvent is optionally MeOH. Embodiment 57 provides the method of any one of Embodiments 50-56, wherein the contacting occurs at a temperature ranging from about 40 °C to about 80 °C. Embodiment 58 provides the method of any one of Embodiments 50-57, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. Embodiment 59 provides a method of promoting a hydroamination reaction between an alkyne and an amine, the method comprising contacting the alkyne and the amine in the presence of the compound of any one of Embodiments 21-40 and optionally in the presence of a Lewis acid. Embodiment 60 provides the method of Embodiment 59, wherein M is Au in the compound of any one of Embodiments 21-40. Embodiment 61 provides the method of Embodiment 59 or 60, wherein the compound of any one of Embodiments 21-40 is present in an amount ranging from about 0.1 to about 10 mol%. Embodiment 62 provides the method of any one of Embodiments 59-61, wherein the alkyne is selected from the group consisting of optionally substituted C 2 -C 12 alkynyl, optionally substituted C 8 -C 12 aralkynyl, and optionally substituted C4-C 12 heteroaralkynyl, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . Embodiment 63 provides the method of any one of Embodiments 59-62, wherein the amine is selected from the group consisting of optionally substituted C4-C 12 heterocycloalkyl comprising at least one secondary amine, H 2 N-NH 2 , H 2 N-N(optionally substituted C 1 -C 6 alkyl) 2 , H 2 N-N(optionally substituted C 1 -C 6 alkyl)(optionally substituted C 4 -C 10 aryl), H 2 N-N(optionally substituted C4-C 10 aryl)2, H2N(optionally substituted C 1 -C 6 alkyl), H2N(optionally substituted C4- C 10 aryl), HN(optionally substituted C 1 -C 6 alkyl)(optionally substituted C 4 -C 10 aryl), HN(optionally substituted C 4 -C 10 aryl) 2 , and NH(optionally substituted C 1 -C 6 alkyl) 2 , wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 - C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C4-C 10 heterocycloalkyl, C 2 -C 6 alkenyl, phenyl, naphthyl, C 4 -C 10 heteroaryl, N(C 1 -C 6 alkyl) 2 , halogen, CN, NO 2, C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 64 provides the method of any one of Embodiments 59-63, wherein the Lewis acid is sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr F ). Embodiment 65 provides the method of any one of Embodiments 59-64, wherein the contacting occurs in the presence of a solvent. Embodiment 66 provides the method of Embodiment 65, wherein the solvent is toluene. Embodiment 67 provides the method of any one of Embodiments 59-66, wherein the contacting occurs at a temperature ranging from about 90 °C to about 110 °C. Embodiment 68 provides the method of any one of Embodiments 59-67, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. Embodiment 69 provides the method of any one of Embodiments 59-68, wherein the contacting of the alkyne and amine provides an imine intermediate. Embodiment 70 provides the method of Embodiment 69, wherein a reduction reaction is promoted by contacting the imine intermediate and a reducing agent. Embodiment 71 provides the method of Embodiment 70, wherein the reducing agent is sodium triacetoxyborohydride (NaBH(OAc)3). Embodiment 72 provides a method of promoting hydration of an alkyne, the method comprising contacting the alkyne and water in the presence of the compound of any one of Embodiments 21-40 and optionally in the presence of a Lewis acid. Embodiment 73 provides the method of Embodiment 72, wherein M is Au in the compound of any one of Embodiments 21-40. Embodiment 74 provides the method of Embodiment 72 or 73, wherein the compound of any one of Embodiments 21-40 is present in an amount ranging from about 0.01 to about 1 mol%. Embodiment 75 provides the method of any one of Embodiments 72-74, wherein the alkyne is selected from the group consisting of optionally substituted C 2 -C 12 alkynyl, optionally substituted C 8 -C 12 aralkynyl, and optionally substituted C 4 -C 12 heteroaralkynyl, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH2, N(C 1 -C 6 alkyl)2, halogen, OH, CN, NO2, C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . Embodiment 76 provides the method of any one of Embodiments 72-75, wherein the Lewis acid is AgSbF6. Embodiment 77 provides the method of any one of Embodiments 72-76, wherein the contacting occurs in the presence of a solvent. Embodiment 78 provides the method of Embodiment 77, wherein the solvent is a mixture of 1,4-dioxane and water. Embodiment 79 provides the method of Embodiment 78, wherein the mixture of 1,4- dioxane and water has a ratio of about 10 : 1 to about 0.1 : 1 (1,4-dioxane : water). Embodiment 80 provides the method of any one of Embodiments 72-79, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. Embodiment 81 provides the method of any one of Embodiments 72-80, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. Embodiment 82 provides a method of promoting a reaction between an aryl chloride and a lithium amide, the method comprising contacting the aryl chloride and the lithium amide in the presence of the compound of any one of Embodiments 21-40. Embodiment 83 provides the method of Embodiment 82, wherein M is Pd in the compound of any one of Embodiments 21-40. Embodiment 84 provides the method of Embodiment 82 or 83, wherein the compound of any one of Embodiments 21-40 is present in an amount ranging from about 0.1 to about 10 mol%. Embodiment 85 provides the method of any one of Embodiments 82-84, wherein the lithium amide is prepared by contacting an amine with a second lithium amide. Embodiment 86 provides the method of Embodiment 85, wherein the second lithium amide is lithium hexamethyldisilazide (LiHMDS). Embodiment 87 provides the method of Embodiment 85 or 86, wherein the amine is selected from the group consisting of optionally substituted C 4 -C 12 heterocycloalkyl comprising at least one secondary amine, H 2 N-NH 2 , H 2 N-N(optionally substituted C 1 -C 6 alkyl) 2 , H 2 N- N(optionally substituted C 1 -C 6 alkyl)(optionally substituted C4-C 10 aryl), H2N-N(optionally substituted C4-C 10 aryl)2, H2N(optionally substituted C 1 -C 6 alkyl), H2N(optionally substituted C4- C 10 aryl), HN(optionally substituted C 1 -C 6 alkyl)(optionally substituted C 4 -C 10 aryl), HN(optionally substituted C4-C 10 aryl)2, and NH(optionally substituted C 1 -C 6 alkyl)2, wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 - C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 4 -C 10 heterocycloalkyl, C 2 -C 6 alkenyl, phenyl, naphthyl, C 4 -C 10 heteroaryl, N(C 1 -C 6 alkyl) 2 , halogen, CN, NO 2, C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 88 provides the method of any one of Embodiments 82-87, wherein the aryl chloride is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one chlorine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 89 provides the method of any one of Embodiments 82-88, wherein the contacting occurs in the presence of a solvent. Embodiment 90 provides the method of Embodiment 89, wherein the solvent is 1,4- dioxane. Embodiment 91 provides the method of any one of Embodiments 82-90, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. Embodiment 92 provides the method of any one of Embodiments 82-91, wherein the contacting occurs for a period of time ranging from about 12 to about 24 h. Embodiment 93 provides a method of promoting a reaction between an aryl chloride and an arylmagnesium halide, the method comprising contacting the aryl chloride and the arylmagnesium halide in the presence of the compound of any one of Embodiments 21-40. Embodiment 94 provides the method of Embodiment 93, wherein M is Pd in the compound of any one of Embodiments 21-40. Embodiment 95 provides the method of Embodiment 93 or 94, wherein the compound of any one of Embodiments 21-40 has a concentration of about 0.1 to about 10 mol%. Embodiment 96 provides the method of any one of Embodiments 93-95, wherein the aryl chloride is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one chlorine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, N(C 1 -C 6 alkyl) 2 , halogen, and NO 2 . Embodiment 97 provides the method of any one of Embodiments 93-96, wherein the arylmagnesium halide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with a magnesium halide moiety, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, N(C 1 -C 6 alkyl)2, halogen, and NO2. Embodiment 98 provides the method of any one of Embodiments 93-97, wherein the contacting occurs in the presence of a solvent. Embodiment 99 provides the method of Embodiment 98, wherein the solvent is 1,4- dioxane. Embodiment 100 provides the method of any one of Embodiments 93-99, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. Embodiment 101 provides the method of any one of Embodiments 93-100, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. Embodiment 102 provides a method of promoting a reaction between an aroyl chloride and an aryl boronic acid, the method comprising contacting the aroyl chloride and the aryl boronic acid in the presence of the compound of any one of Embodiments 21-40 and a base. Embodiment 103 provides the method of Embodiment 102, wherein M is Pd in the compound of any one of Embodiments 21-40. Embodiment 104 provides the method of Embodiment 102 or 103, wherein the compound of any one of Embodiments 21-40 is present in an amount ranging from about 0.1 to about 10 mol%. Embodiment 105 provides the method of any one of Embodiments 102-104, wherein the aroyl chloride is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with a C(=O)Cl moiety, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, N(C 1 -C 6 alkyl)2, halogen, CN, NO2, C(=O)O(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 106 provides the method of any one of Embodiments 102-105, wherein the aryl boronic acid is selected from the group consisting of optionally substituted C 6 -C 10 aryl boronic acid and optionally substituted C4-C 10 heteroaryl boronic acid, wherein each optional substituent is at least one selected the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 - C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH2, C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 107 provides the method of any one of Embodiments 102-106, wherein the base is K 2 CO 3 . Embodiment 108 provides the method of any one of Embodiments 102-107, wherein the reaction occurs in the presence of a solvent. Embodiment 109 provides the method of Embodiment 108, wherein the solvent is 1,4- dioxane. Embodiment 110 provides the method of any one of Embodiments 102-109, wherein the contacting occurs at a temperature ranging from about 80 °C to about 100 °C. Embodiment 111 provides the method of any one of Embodiments 102-110, wherein the contacting occurs for a period of time ranging from about 8 h to about 24 h. Embodiment 112 provides a method of promoting a reaction between an aryl iodide, an aniline, and carbon monoxide (CO), the method comprising contacting the aryl iodide, the aniline, and the CO in the presence of the compound of any one of Embodiments 21-40 and a base. Embodiment 113 provides the method of Embodiment 112, wherein M is Pd in the compound of any one of Embodiments 21-40. Embodiment 114 provides the method of Embodiment 112 or 113, wherein the compound of any one of Embodiments 21-40 is present in an amount ranging from about 0.1 to about 10.0 mol%. Embodiment 115 provides the method of any one of Embodiments 112-114, wherein the aryl iodide is selected from the group consisting of optionally substituted C 6 -C 10 aryl and optionally substituted C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one iodine atom, and wherein each optional substituent is at least one selected from the group consisting of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl)2. Embodiment 116 provides the method of any one of Embodiments 112-115, wherein the aniline is selected from the group consisting of optionally substituted C 6 -C 10 aryl and C 2 -C 10 heteroaryl, wherein the aryl or heteroaryl is substituted with at least one NH 2 , and wherein each optional substituent is at least one selected from the group consisting of of C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 , haloalkyl, C 1 -C 6 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 10 heterocyclyl, C 2 -C 6 alkenyl, phenyl, naphthyl, NH 2 , N(C 1 -C 6 alkyl) 2 , halogen, OH, CN, NO 2 , C(=O)OH, C(=O)O(C 1 -C 6 alkyl), C(=O)NH 2 , C(=O)NH(C 1 -C 6 alkyl), and C(=O)N(C 1 -C 6 alkyl) 2 . Embodiment 117 provides the method of any one of Embodiments 112-116, wherein the CO has a pressure ranging from about 0.1 to about 10 atm. Embodiment 118 provides the method of any one of Embodiments 112-117, wherein the base is K3PO4. Embodiment 119 provides the method of any one of Embodiments 112-118, wherein the contacting occurs in the presence of a solvent. Embodiment 120 provides the method of Embodiment 119, wherein the solvent is toluene. Embodiment 121 provides the method of any one of Embodiments 112-120, wherein the contacting occurs at a temperature ranging from about 90 °C to about 110 °C. Embodiment 122 provides the method of any one of Embodiments 112-121, wherein the contacting occurs for a period of time ranging from about 8 to about 24 h. Embodiment 123 provides a method of preparing 2-(2,6-diisopropylphenyl)-5- (dimethylamino)imidazo[1,5-a]pyridin-2-ium chloride) (1): the method comprising reacting (E)-6-(((2,6-diisopropylphenyl)imino)methyl)-N,N- dimethylpyridin-2-amine (A): and paraformaldehyde so as to generate a first reaction system comprising (1). Embodiment 124 provides the method of Embodiment 123, wherein the reaction of (Z) and paraformaldehyde is performed in the presence of a solvent. Embodiment 125 provides the method of Embodiment 124, wherein the solvent is EtOH. Embodiment 126 provides the method of any one of Embodiments 123-125, further comprising hydrochloric acid (HCl). Embodiment 127 provides the method of any one of Embodiments 123-126, wherein the reaction of (Z) and paraformaldehyde is performed at a temperature of about 70 °C. Embodiment 128 provides the method of any one of Embodiments 123-127, wherein the (Z) is prepared by reacting 6-(dimethylamino)picolinaldehyde (Y): and 2,6-diisopropylaniline (X): Embodiment 129 provides the method of Embodiment 128, wherein the reaction of (Y) and (X) is performed in the presence of a solvent. Embodiment 130 provides the method of Embodiment 129, wherein the solvent is EtOH. Embodiment 131 provides the method of any one of Embodiments 128-130, wherein the reaction of (Y) and (X) is performed at a temperature of about 90 °C. Embodiment 132 provides the method of any one of Embodiments 128-131, wherein the (Y) is prepared by reacting 6-bromo-N,N-dimethylpyridin-2-amine (W): and an organolithium reagent to form a lithiated intermediate, and contacting the lithiated intermediate with a formylating reagent. Embodiment 133 provides the method of Embodiment 132, wherein the reaction of (W) and the organolithium reagent is performed in the presence of a solvent. Embodiment 134 provides the method of Embodiment 133, wherein the solvent is tetrahydrofuran (THF). Embodiment 135 provides the method of any one of Embodiments 132-134, wherein the organolithium reagent is n-butyllithium (n-BuLi). Embodiment 136 provides the method of any one of Embodiments 132-135, wherein the reaction of (W) and the organolithium reagent is performed at about -78 °C. Embodiment 137 provides the method of any one of Embodiments 132-136, wherein the reaction of the lithiated intermediate and the formylating reagent is performed in the presence of a solvent. Embodiment 138 provides the method of Embodiment 137, wherein the solvent is tetrahydrofuran (THF). Embodiment 139 provides the method of any one of Embodiments 132-138, wherein the formylating agent is dimethylformamide (DMF). Embodiment 140 provides the method of any one of Embodiments 132-139, wherein the contacting occurs at a temperature of about -78 °C. Embodiment 141 provides the method of any one of Embodiments 132-136, wherein the (W) is prepared by reacting (V): and dimethylamine (HNMe 2 ), in the presence of a base. Embodiment 142 provides the method of Embodiment 141, wherein the reaction of (V) and dimethylamine is performed in the presence of a solvent. Embodiment 143 provides the method of Embodiment 142, wherein the solvent is acetonitrile (ACN). Embodiment 144 provides the method of any one of Embodiments 141-143, wherein the base is K 2 CO 3 . Embodiment 145 provides the method of any one of Embodiments 141-144, wherein the reaction of (V) and dimethylamine is performed at a temperature of about 100 °C. The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this disclosure has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this disclosure may be devised by others skilled in the art without departing from the true spirit and scope of the disclosure. The appended claims are intended to be construed to include all such embodiments and equivalent variations.
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