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Abstract

The development of earth-abundant catalysts for the selective conversion of silanes to silanols with water as an oxidant generating valuable hydrogen as the only by-product continues to be a challenge. Here, we demonstrate that [MnBr(CO)₅] is a highly active precatalyst for this reaction, operating under neutral conditions and avoiding the undesired formation of siloxanes. As a result, a broad substrate scope, including primary and secondary silanes, could be converted to the desired products. The turnover performances of the catalyst were also examined, yielding a maximum TOF of 4088 h⁻¹. New light was shed on the debated mechanism of the interaction between [MnBr(CO)₅] and Si–H bonds based on the reaction kinetics (including KIEs of PhMe₂SiD and D₂O) and spectroscopic techniques (FT-IR, GC-TCD, ¹H-, ²⁹Si-, and ¹³C-NMR). The initial activation of [MnBr(CO)₅] was found to result from the formation of a manganese(I) hydride species and R₃SiBr, and the experimental data are most consistent with a catalytic cycle comprising a cationic tricarbonyl Mn(I) unit as the active framework.