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

Shintaro IshidaTakuroh HatakeyamaTakuya NomuraMaiko MatsumotoKimio YoshimuraSoichiro KyushinTakeaki Iwamoto
Published in: Chemistry (Weinheim an der Bergstrasse, Germany) (2020)
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.
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