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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
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja045078kDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja045078kPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja045078kPublisherSupporting Information
ORCID:
AuthorORCID
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 AgencyGrant Number
BP MC2 programUNSPECIFIED
NIH Predoctoral FellowshipUNSPECIFIED
National Cancer InstituteUNSPECIFIED
Issue or Number:46
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
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
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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