title: Long-range C-H bond activation by Rh(III)-carboxylates.
abstract: Traditional C-H bond activation by a concerted metalation-deprotonation (CMD) mechanism involves precoordination of the C-H bond followed by deprotonation from an internal base. Reported herein is a "through-arene" activation of an uncoordinated benzylic C-H bond that is 6 bonds away from a Rh(III) ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectroscopically upon addition of a pyridine base to provide a thermodynamic trap.
authors.affiliation: Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904-4319, United States.
authors.forename: Matthew E
authors.initials: ME
authors.lastname: O'Reilly
authors.forename: Ross
authors.initials: R
authors.lastname: Fu
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Nielsen
authors.forename: Michal
authors.initials: M
authors.lastname: Sabat
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.forename: T Brent
authors.initials: TB
authors.lastname: Gunnoe