A Six‐Coordinate Silicon Dihydride Embedded in a Porphyrin: Enhanced Hydride‐Donor Properties and the Catalyst‐Free Hydrosilylation of CO2

The catalyst-free hydrosilylation of CO2 under mild conditions remains limited. Herein, we report the synthesis, characterization, and reactivity of 5,10,15,20-tetraphenylporphyrinato(dihydrido)silicon(IV) (1) as a six-coordinate silicon dihydride. The Si-H moiety of 1 reacts with polar double bonds and CO2 in the absence of a catalyst to afford hydrosilylated products. Combining the hydrosilylation with subsequent transformation furnishes formic acid from CO2 . Computational studies indicate that the hydride-donor properties of 1 are exceptionally high for a neutral silicon hydride, and that the direct hydride transfer from silicon to carbon is a pivotal step in the hydrosilylation of CO2 with 1.