Facile Deoxygenative Reduction of a Bridging Carbonato Ligand with Silyl and Boryl 4,4’‐Bipyridinylidene Reagents

Abstract

AbstractThe reactivity of CO2 with a previously described PCcarbeneP cobalt(I) hydroxide is reported. Insertion of CO2 into the Co−OH bond followed by a dehydration reaction releasing water results in a cobalt(I) bridging carbonate species featuring fluctional κ1: κ1 and κ1: κ2 coordination of the central carbonate moiety. The reduction chemistry of the resulting cobalt(I) bridging carbonate species is explored utilizing deoxygenative reducing agents N,N′‐bis(trimethylsilyl)‐ and N,N′‐bis(pinacolatoboryl)‐4,4′‐bipyridinylidene. The three‐electron reduction produces the corresponding PCcarbeneP cobalt(I) siloxide or boroxide complex alongside a PCcarbeneP cobalt(0) monocarbonyl, silyl/boryl ether, and 4,4’‐bipyridine.