Selective catalytic Frustrated Lewis Pair Hydrogenation of CO2 in the Presence of Silylhalides

The 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.