Kinetic and Thermodynamic Preferences in Aryl vs Benzylic C−H Bond Activation with Cationic Pt(II) Complexes

Heyduk, Alan F. and Driver, Tom G. and Labinger, Jay A. and Bercaw, John E. (2004) Kinetic and Thermodynamic Preferences in Aryl vs Benzylic C−H Bond Activation with Cationic Pt(II) Complexes. Journal of the American Chemical Society, 126 (46). pp. 15034-15035. ISSN 0002-7863. doi:10.1021/ja045078k. https://resolver.caltech.edu/CaltechAUTHORS:20170420-084321419

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Abstract

Anhydrous cationic Pt(II) complexes [(NN)Pt(CH_3)(CF_3CD_2OD)]+ (1, NN = ArNC(Me)−C(Me)NAr), which are obtained by reaction of (NN)Pt(CH_3)_2 with B(C_6F_5)_3 in CF_3CD_2OD, activate C−H bonds of benzene and methylbenzenes, with enhanced reactivity compared to the previously prepared equilibrium mixtures with the (thermodynamically favored) aquo complexes. For methylbenzenes (toluene, p-xylene, mesitylene), activation at the aromatic and benzylic positions are kinetically competitive, but the product of the latter is strongly favored thermodynamically. This unusual trend is attributed to formation of η^3-benzyl structures, which can be observed spectroscopically for 1,4-diethylbenzene activation.

Item Type:

Article

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URL	URL Type	Description
http://dx.doi.org/10.1021/ja045078k	DOI	Article
http://pubs.acs.org/doi/abs/10.1021/ja045078k	Publisher	Article
http://pubs.acs.org/doi/suppl/10.1021/ja045078k	Publisher	Supporting Information

ORCID:

Author	ORCID
Labinger, Jay A.	0000-0002-1942-9232

Additional Information:

© 2004 American Chemical Society. Received 16 August 2004. Published online 28 October 2004. Published in print 1 November 2004. Funding for this work was provided by the BP MC2 program and the NIH in the form of an NCI fellowship to A.F.H. and an NRSA fellowship to T.G.D. We thank Dr. Scott Ross for assistance with NMR spectrometry, Dr. Mona Shahgholi for mass spectrometry data, and Mr. Larry M. Henling for crystallographic analysis.

Funders:

Funding Agency	Grant Number
BP MC2 program	UNSPECIFIED
NIH Predoctoral Fellowship	UNSPECIFIED
National Cancer Institute	UNSPECIFIED

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DOI:

10.1021/ja045078k

Record Number:

CaltechAUTHORS:20170420-084321419

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20170420-084321419

Official Citation:

Kinetic and Thermodynamic Preferences in Aryl vs Benzylic C−H Bond Activation with Cationic Pt(II) Complexes Alan F. Heyduk, Tom G. Driver, Jay A. Labinger, and John E. Bercaw Journal of the American Chemical Society 2004 126 (46), 15034-15035 DOI: 10.1021/ja045078k

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ID Code:

76753

Collection:

CaltechAUTHORS

Deposited By:

Ruth Sustaita

Deposited On:

20 Apr 2017 18:44

Last Modified:

15 Nov 2021 17:02

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