Carbon Dioxide Hydrosilylation to Methane Catalyzed by Zinc and Other First-Row Transition Metal Salts

We accomplished zinc catalyzed hydrosilylation of carbon dioxide (CO2) to silyl formate (C+II), bis(silyl)acetal (C0), methoxysilane (C−II), and finally methane (C−IV). Among several zinc salts, we found that Zn(OAc)2 with ligand 1,10-phenanthroline was the best. A turnover number of 815000 was achieved using the zinc catalyst to yield C+II. Unexpectedly, we observed the generation of CO from CO2 and hydrosilane for the first time. In addition to Zn, other first-row transition metals (Mn, Fe, Co, Ni, and Cu) also served as Lewis acid catalysts for CO2 hydrosilylation, regardless of the nature of the metal.