A 1,2,3-triazole-derived pincer-type mesoionic carbene complex of iron(II): carbonyl elimination and hydrosilylation of aromatic aldehydes via the concerted reaction with hydrosilane and a base.

Abstract

Iron complexes bearing 1,2,3-triazol-5-ylidene were synthesized and applied to the reaction with hydrosilane and homogeneous catalytic hydrosilylation of aromatic ketones and aldehydes. Addition of a free carbene to a solution of Fe(CO)4Br2 yielded an octahedral, diamagnetic and cationic iron(II) complex [Fe(1,2,3-triazolylidene)(CO)2Br]+. Pyrolysis of the dicarbonyl complex eliminated the two CO ligands to form a paramagnetic four-coordinate complex. A theoretical study using DFT calculations indicated that the spin state changed from singlet to quintet during ligand elimination. Investigations of the successful hydrosilylation of acetophenone and benzaldehyde derivatives using MIC-iron(II) bromide suggested the importance of the base for efficient conversion in the catalytic process. The bromide-to-hydride exchange reaction, transmetallation, of MIC-iron(II) bromide in the presence of KOtBu and HSi(OEt)3 which could occur in the initial process of hydrosilylation was proposed, and supported by a theoretical study.