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Published October 22, 2014 | Version Supplemental Material
Journal Article Open

Long-Range C–H Bond Activation by Rh^(III)-Carboxylates

Creators

  • 1. ROR icon University of Virginia
  • 2. ROR icon California Institute of Technology

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.

Additional Information

© 2014 American Chemical Society. Received: August 14, 2014; Published: October 10, 2014. The authors acknowledge support from the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001298. We thank Thomas Rey for assistance with the single crystal X-ray diffraction experiments.

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Supplemental Material - ja508367m_si_001.pdf

Supplemental Material - ja508367m_si_002.cif

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Additional details

Additional titles

Alternative title
Long-Range C–H Bond Activation by RhIII-Carboxylates

Identifiers

Eprint ID
52255
Resolver ID
CaltechAUTHORS:20141202-075224286

Funding

Department of Energy (DOE)
DE-SC0001298

Dates

Created
2014-12-02
Created from EPrint's datestamp field
Updated
2023-03-16
Created from EPrint's last_modified field