Direct Spectroscopic Characterization of a Transitory Dirhodium Donor-Acceptor Carbene Complex

Katherine P. Kornecki, John F. Briones, Vyacheslav Boyarskikh, Felicia Fullilove, Jochen Autschbach, Kaitlin E. Schrote, Kyle M. Lancaster, Huw M. L. Davies, and John F. Berry

2013, 342, 351-354; 10.1126/science.1243200


A detailed understanding of a reaction mechanism is key to the development and refinement of said reaction. This collaborative project between CCHF members Huw Davies (Emory University), and John Berry (University of Wisconsin at Madison), and external investigators Jochen Autschbach (State University of New York at Buffalo), and Kyle Lancaster (Cornell University), brought together the expertise required to isolate and characterize the donor/acceptor substituted dirhodium carbenoid for the first time.

The information gathered from these inter-disciplinary studies will have significant implications for the field of catalysis and in particular C–H Functionalization. Direct evidence for this intermediate has not been described since Teyssie and co-workers first reported the reaction of Rh2(OAc)4 and ethyl diazoacetate forty years ago.

Without this experimental evidence previous models and theories have relied on theoretical and computational explanations. These studies will provide the experimental foundation upon which future reactions will be developed, leading both the theoretical and experimental studies.

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