Generation of dihydrogen molecule and hydrosilylation of carbon dioxide catalyzed by zinc hydride complex: theoretical understanding and prediction.

Abstract

Generation of H2 from methanol/water and hydrosilylation of CO2 catalyzed by [tris(2-pyridylthio)methyl]zinc hydride [κ(3)-Tptm]ZnH 1 were investigated with DFT and MP2 methods. The hydrosilylation of CO2 occurs via the CO2 insertion into the Zn-H bond of 1 followed by the metathesis of a Zn-(η(1)-OCOH) bond with hydrosilane to yield silyl formate and regenerate 1. The CO2 insertion easily occurs, but the metathesis is difficult because of the formation of a very stable Zn-(η(2)-O2CH) species before the metathesis. The ΔG°(‡) value of the metathesis with triethoxysilane is much smaller than that with phenylsilane because electronegative methoxy groups stabilize the transition state bearing hypervalent Si center, which is consistent with the experimental result that triethoxysilane is used in the hydrosilylation of CO2. It is theoretically predicted here that hydrosilane with two electronegative OEt groups or one to three F groups can be applied to this reaction. In the generation of H2 from methanol/water by 1, the first step is the metathesis of 1 with the O-H bond of methanol/water to produce [κ(3)-Tptm]Zn(OMe)/[k(3)-Tptm]Zn(OH) and dihydrogen molecule. The next step is the metathesis of the Zn-OMe/Zn-OH bond with hydrosilane to yield silyl ether and regenerate 1. The first metathesis is rate-determining but the second one occurs with very small activation energy, indicating that various hydrosilanes can be applied to this reaction.