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Two new [Ir(NHC)(COD)Cl] (NHC = N-heterocyclic carbene; COD = 1,5-cyclooctadiene) iridium complexes (2a,b) have been prepared by the reaction of [Ir(COD)Cl]2 with in situ prepared NHC-Ag carbene transfer agents in dichloromethane at ambient temperature. They have been fully characterized by (1)H, (13)C NMR, and elemental analysis. X-ray diffraction studies on single crystals of 2a and 2b confirm the square planar geometry. Complexes of type [Ir(NHC)(CO)2Cl] [NHC = 1,3-diisopropyl(5,6-dimethyl)benzimidazol-2-ylidene] 3 were also synthesized to compare σ-donor/π-acceptor strength of NHC ligands. Transfer hydrogenation (TH) reactions of various aldehydes and ketones have been studied using complexes 2a and 2b as catalysts. The 5,6-dimethyl substituted iridium complex (2b) showed the highest catalytic activity for the TH reaction.

Iridium(I) complexes of N-heterocyclic carbenes (NHCs) (1a-3a) were obtained by transmetalation reactions from the corresponding Ag(I)-NHC complexes. These complexes have been fully characterized by (1)H, (13)C, heteronuclear multiple-bond correlation NMR spectroscopies, and elemental analysis. X-ray diffraction studies on single crystals of 1a and 2a confirm the square planar geometry at the metal center. [IrCl(CO)2(NHC)] complexes 1b-3b were also synthesized to compare σ-donor/π-acceptor strength of NHC ligands. Transfer hydrogenation (TH) reactions of various ketones and imines have been studied using complexes 1a-3a as precatalysts. N-Benzyl substituted NHC complexes of Ir(I) proved to be highly efficient precatalysts in the reduction of aromatic and aliphatic ketones to afford the corresponding alcohol products with turnover frequencies values up to 24,000 h(-1).

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