The new air-stable and moisture-insensitive Ir catalysts for efficient transfer hydrogenation of ketones contain a chelating bis(N-heterocyclic carbene) ligand. Most other hydrogen transfer catalysts show activity Rh > Ir, but we find Ir > Rh for these cases. Tuning of the ligand wingtip substituents, R, can greatly increase catalyst activity (R = neopentyl) or selectivity (R = isopropyl). Reactivity studies and isotopic labeling are consistent with a monohydride mechanism for the hydrogen transfer.

Chelating bis(imidazolium) salts having (CH 2 ) n chains of different lengths (n ) 1-4) linking the diazole rings show very large reactivity differences on metalation with [(cod)RhCl] 2 . Long linkers favor a square-planar Rh(I) product, while short linkers favor octahedral Rh(III). We ascribe the origin of the effect to the restricted rotation of the highly sterically anisotropic diazole rings and the different preferred orientations of these rings as n changes. Defining the x and y axes as the Rh-carbene bond directions, we find that with short linkers the diazole rings tend to be oriented close to the xy plane. This tends to favor Rh(III) because these complexes, [Rh(bis-carbene)I 2 (OAc)], have the lowest steric hindrance in the xy plane. With long linkers, the diazole rings tend to be aligned face to face along the (z axis. This tends to favor Rh(I) because these complexes, [(cod)Rh(bis-carbene)]PF 6 , have the lowest steric hindrance along the (z axis. Crystallographic studies are reported. Electrospray MS data provide evidence for strong metal-carbene binding.

Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir(III), not Ir(V), because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. 19F,1H-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)).