Hydrolysis and Methanolysis of Silanes Catalyzed by Iridium(III) Bis-N-Heterocyclic Carbene Complexes: Influence of the Wingtip Groups

New [Ir(CH 3 CN) 2 (I) 2 {κ C, C ′-bis(NHC)}]BF 4 complexes featuring bis-NHC ligands with a methylene bridge and different N substitution (−CH 2 CH 2 CH 2 CH 3 and −CH 2 CH 2 OPh) were synthesized. NMR studies and X-ray diffraction structures evidenced that the wingtip group −CH 2 CH 2 OPh presents a hemilabile behavior in solution, with the oxygen atom coordinating and dissociating at room temperature, which contrasts with the strong coordination of the ether functions in the complex [Ir(I) 2 {κ C, C ′, O, O ′-bis(NHC OMe )}]BF 4 (bis(NHC OMe ) = methylenebis( N, N ′-bis(2-methoxyethyl)imidazol-2-ylidene)), previously reported by us. These complexes proved to be efficient catalysts for the hydrolysis and methanolysis of silanes, affording molecular hydrogen and silyl alcohols or silyl ethers as the main reaction products in excellent yields. The hydrogen generation rates were very much dependent on the nature of the hydrosilane and the coordination ability of the wingtip group. The latter also played a key role in the recyclability of the catalytic system.