Reduction of Carbon Oxides by an Acyclic Silylene: Reductive Coupling of CO

C−C Coupling: Reactions of a boryl‐substituted acyclic silylene with CO₂ and CO are reported. The former proceeds through O‐atom abstraction (generating CO), the latter via reductive coupling of CO to give [OCCO]²⁻, which undergoes formal insertion into the Si−B bond. The net reaction of CO₂ with two equivalents of silylene can therefore be shown to constitute a three‐electron reduction of CO₂ to [C₂O₂]²⁻.

Abstract

Reactions of a boryl‐substituted acyclic silylene with carbon dioxide and monoxide are reported. The former proceeds through oxygen atom abstraction, generating CO (with rearrangement of the putative silanone product through silyl‐group transfer). The latter is characterized by reductive coupling of CO to give an ethynediolate fragment, which undergoes formal insertion into the Si−B bond. The net conversion of carbon dioxide with two equivalents of silylene offers a route for the three‐electron reduction of CO₂ to [C₂O₂]²⁻.

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