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Bimetallic, Silylene‐Mediated Multielectron Reductions of Carbon Dioxide and Ethylene
Author(s) -
Whited Matthew T.,
Zhang Jia,
Conley Anna M.,
Ma Senjie,
Janzen Daron E.,
Kohen Daniela
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202011489
Subject(s) - silylene , ethylene , chemistry , bimetallic strip , cobalt , ligand (biochemistry) , photochemistry , steric effects , cationic polymerization , cycloaddition , molecule , metal , redox , catalysis , silicon , inorganic chemistry , polymer chemistry , organic chemistry , biochemistry , receptor
A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R 2 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 CO 2 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 3 d metals.