Cationic Iridium Complexes Bearing Imidazol-2-ylidene Ligands as Transfer Hydrogenation Catalysts

The synthesis and characterization by X-ray crystallography of the complexes [Ir(cod)(py)(L)]PF6 (L = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (2); L = IPr, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (3); L = ICy, 1,3-bis(cyclohexyl)imidazol-2-ylidene (4)) are reported. Complexes 2−4 have been employed as catalysts for transfer hydrogenation reactions from 2-propanol to a number of unsaturated substrates and their activity compared with that of the related cationic iridium(I) species [Ir(cod)(py)(SIMes)]PF6 (1), [Ir(cod)(py)(PCy3)]PF6 (5), and complexes formed in situ from [Ir(cod)(py)2]PF6 and diazabutadienes (RNCHCHNR, DAB-R; R = cyclohexyl, DAB-Cy; R = 2,4,6-trimethylphenyl, DAB-Mes; R = adamantyl, DAB-Ad; R = 2,4,6-trimethoxyphenyl, DAB-trimethoxyphenyl). All complexes tested were found to be active catalysts for transfer hydrogenation of ketones, with complex 4 displaying the highest activity. Complex 4 also exhibits moderate activity toward simple olefins and an aromatic nitro compound.