Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 3, Pages 1615-1619Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202011489
Keywords
carbon dioxide fixation; cobalt; density-functional calculations; redox chemistry; reduction
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Funding
- CAREER award from the National Science Foundation [CHE-1552591]
- NSF-MRI [1428752, 1125975]
- NSF-MRI award through the Midwest Undergraduate Computational Chemistry Consortium (MU3C) [CHE-1919571]
- Riecker Endowed Fund for the Sciences at Carleton College
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1428752] Funding Source: National Science Foundation
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The research demonstrates a metal/ligand cooperative approach to reducing small molecules using metal silylene complexes, achieving net two-electron transformations through one-electron redox processes. Silicon activates incoming substrates and mediates the generation of bimetallic products with two metal centers, suitable for 3d metals.
A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R2Si=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 Co-II 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 Co-II/Co-II 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.
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