Published October 22, 2014
| Supplemental Material
Journal Article
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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.
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.Attached Files
Supplemental Material - ja508367m_si_001.pdf
Supplemental Material - ja508367m_si_002.cif
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Additional details
- Alternative title
- Long-Range C–H Bond Activation by RhIII-Carboxylates
- Eprint ID
- 52255
- Resolver ID
- CaltechAUTHORS:20141202-075224286
- DE-SC0001298
- Department of Energy (DOE)
- Created
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2014-12-02Created from EPrint's datestamp field
- Updated
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2023-03-16Created from EPrint's last_modified field