Characterization of Tunable Radical Metal–Carbenes: Key Intermediates in Catalytic Cyclopropanation
- 29 April 2011
- journal article
- research article
- Published by American Chemical Society (ACS) in Organometallics
- Vol. 30 (10) , 2739-2746
- https://doi.org/10.1021/om2001348
Abstract
A new class of radical metal–carbene complex has been characterized as having Fischer-like orbital interactions and adjacent π acceptor stabilization. Density functional theory along with natural bond orbital analysis and charge decomposition analysis has given insight into the electronics of this catalytic intermediate in an open-shell cobalt–porphyrin, [Co(Por)], system. The complex has a single bond from the metal to the carbene and has radical character with localized spin density on the carbene carbon. In addition, the carbene carbon is found to be nucleophilic and “tunable” through the introduction of different α-carbon substituents. Finally, based on these findings, rational design strategies are proposed that should lead to the enhancement of catalytic activity.This publication has 75 references indexed in Scilit:
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