Long-range C-H bond activation by RhIII-carboxylates

Matthew E. O'Reilly; Ross Fu; Robert J. Nielsen; Michal Sabat; William A. Goddard; T. Brent Gunnoe

doi:10.1021/ja508367m

Long-range C-H bond activation by Rh^III-carboxylates

Matthew E. O'Reilly
, Ross Fu
, Robert J. Nielsen
, Michal Sabat
, William A. Goddard
, T. Brent Gunnoe

Department of Chemistry
University of Virginia
Materials and Process Simulation Center
California Institute of Technology
Nanoscale Materials Characterization Facility
University of Virginia School of Engineering and Applied Science

Research output: Contribution to journal › Article › peer-review

26 Citations (Scopus)

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.

Original language	English
Pages (from-to)	14690-14693
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	42
DOIs	https://doi.org/10.1021/ja508367m
Publication status	Published - 1 Nov 2014
Externally published	Yes

Access to Document

10.1021/ja508367m

Cite this

@article{1946c831019e4ce09b9a867566fbe3ea,

title = "Long-range C-H bond activation by RhIII-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 RhIII 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.",

author = "O'Reilly, \{Matthew E.\} and Ross Fu and Nielsen, \{Robert J.\} and Michal Sabat and Goddard, \{William A.\} and Gunnoe, \{T. Brent\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = nov,

day = "1",

doi = "10.1021/ja508367m",

language = "English",

volume = "136",

pages = "14690--14693",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "42",

}

TY - JOUR

T1 - Long-range C-H bond activation by RhIII-carboxylates

AU - O'Reilly, Matthew E.

AU - Fu, Ross

AU - Nielsen, Robert J.

AU - Sabat, Michal

AU - Goddard, William A.

AU - Gunnoe, T. Brent

PY - 2014/11/1

Y1 - 2014/11/1

N2 - 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 RhIII 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.

AB - 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 RhIII 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.

U2 - 10.1021/ja508367m

DO - 10.1021/ja508367m

M3 - Article

AN - SCOPUS:84908431040

SN - 0002-7863

VL - 136

SP - 14690

EP - 14693

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 42

ER -

Long-range C-H bond activation by RhIII-carboxylates

Abstract

Access to Document

Fingerprint

Cite this

Long-range C-H bond activation by Rh^III-carboxylates