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Large Kinetic Isotope Effects for the Protonolysis of Metal-Methyl Complexes Are Not Reliable Mechanistic Indicators

Scott, Valerie J. and Labinger, Jay A. and Bercaw, John E. (2011) Large Kinetic Isotope Effects for the Protonolysis of Metal-Methyl Complexes Are Not Reliable Mechanistic Indicators. Organometallics, 30 (16). pp. 4374-4378. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20110912-114655621

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Abstract

Earlier work on protonolyses of several palladium and platinum methyl complexes (with release of methane) had suggested the possibility that observation of an unusually large kinetic isotope effect, consistent with significant contributions from quantum mechanical tunneling, might be diagnostic of a mechanism involving direct protonation of the metal–methyl bond, as opposed to one proceeding via a metal hydride intermediate. By extension of these measurements to a wider set of complexes, we find no support for the proposed correlation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om200432bDOIArticle
http://pubs.acs.org/doi/full/10.1021/om200432bPublisherArticle
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2011 American Chemical Society. Received: May 23, 2011. Publication Date (Web): July 18, 2011. This research was funded by BP through the Methane Conversion Cooperative (MC2) program. We thank M. Findlater and M. Brookhart for providing the PONOP complexes and Dr. David Vander Velde for help with NMR experiments.
Funders:
Funding AgencyGrant Number
BP MC2 programUNSPECIFIED
Issue or Number:16
Record Number:CaltechAUTHORS:20110912-114655621
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110912-114655621
Official Citation:Large Kinetic Isotope Effects for the Protonolysis of Metal–Methyl Complexes Are Not Reliable Mechanistic Indicators Valerie J. Scott, Jay A. Labinger, John E. Bercaw Organometallics 2011 30 (16), 4374-4378
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:25303
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:13 Sep 2011 21:42
Last Modified:03 Oct 2019 03:04

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