Selective Catalytic Frustrated Lewis Pair Hydrogenation of CO(2) in the Presence of Silylhalides

The frustrated Lewis pair (FLP) derived from 2,6‐lutidine and B(C(6)F(5))(3) is shown to mediate the catalytic hydrogenation of CO(2) using H(2) as the reductant and a silylhalide as an oxophile. The nature of the products can be controlled with the judicious selection of the silylhalide and the solvent. In this fashion, this metal‐free catalysis affords avenues to the selective formation of the disilylacetal (R(3)SiOCH(2)OSiR(3)), methoxysilane (R(3)SiOCH(3)), methyliodide (CH(3)I) and methane (CH(4)) under mild conditions. DFT studies illuminate the complexities of the mechanism and account for the observed selectivity.