CaltechAUTHORS
  A Caltech Library Service

Mechanism of C−H Bond Activation of Alkyl-Substituted Benzenes by Cationic Platinum(II) Complexes

Driver, Tom G. and Day, Michael W. and Labinger, Jay A. and Bercaw, John E. (2005) Mechanism of C−H Bond Activation of Alkyl-Substituted Benzenes by Cationic Platinum(II) Complexes. Organometallics, 24 (15). pp. 3644-3654. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20170725-152201084

[img] PDF (Detailed experimental procedures, characterization data, integrated rate laws, tables of GC-MS isotope exchange, and X-ray diffraction data for 12) - Supplemental Material
See Usage Policy.

841Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

22Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170725-152201084

Abstract

While all methyl- and ethyl-substituted benzenes react with diimine Pt(II) methyl cations to give η^3-benzyl products, they do not all get there by the same pathway. For toluene and p-xylene, isotopic labeling shows that initial activation occurs at aryl positions with subsequent intermolecular conversion to the benzyl product. For ethylbenzene and 1,4-diethylbenzene, initial activation takes place exclusively at aryl C−H bonds, and conversion to the η^3-benzyl product takes place via intramolecular isomerization. Only in the most extreme case of steric crowding the reaction of a bulky diimine platinum methyl cation (Ar = Mes) with triethylbenzene does direct activation of the ethyl group become preferred to aryl activation.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/om050251mDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om050251mPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om050251mPublisherSupporting Information
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2005 American Chemical Society. Received April 4, 2005. Publication Date (Web): June 22, 2005. Funding for this work was provided by the bp MC2 program and the NIH in the form of a NRSA fellowship to T.G.D. (GM070272-02). We thank Jonathan S. Owen for insightful discussions, 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
NIHGM070272-02
Issue or Number:15
Record Number:CaltechAUTHORS:20170725-152201084
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170725-152201084
Official Citation:Mechanism of C−H Bond Activation of Alkyl-Substituted Benzenes by Cationic Platinum(II) Complexes Tom G. Driver, Michael W. Day,Jay A. Labinger, and John E. Bercaw. Organometallics 2005 24 (15), 3644-3654 DOI: 10.1021/om050251m
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79355
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Jul 2017 22:34
Last Modified:03 Oct 2019 18:19

Repository Staff Only: item control page