A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R2 Si=M) is demonstrated, whereby silicon activates the incoming substrate and mediates net two-electron transformations by one-electron redox processes at two metal centers. An appropriately tuned cationic pincer cobalt(I) complex, featuring a central silylene donor, reacts with CO2 to afford a bimetallic siloxane, featuring two CoII centers, with liberation of CO; reaction of the silylene complex with ethylene yields a similar bimetallic product with an ethylene bridge. Experimental and computational studies suggest a plausible mechanism proceeding by [2+2] cycloaddition to the silylene complex, which is quite sensitive to the steric environment. The CoII /CoII products are reactive to oxidation and reduction. Taken together, these findings demonstrate a strategy for metal/ligand cooperative small-molecule activation that is well-suited to 3d metals.
Keywords: carbon dioxide fixation; cobalt; density-functional calculations; redox chemistry; reduction.
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