CaltechAUTHORS
  A Caltech Library Service

Mechanism of Ru(II)-Catalyzed Olefin Insertion and C−H Activation from Quantum Chemical Studies

Oxgaard, Jonas and Goddard, William A., III (2004) Mechanism of Ru(II)-Catalyzed Olefin Insertion and C−H Activation from Quantum Chemical Studies. Journal of the American Chemical Society, 126 (2). pp. 442-443. ISSN 0002-7863. doi:10.1021/ja038399p. https://resolver.caltech.edu/CaltechAUTHORS:20170419-130606747

[img] PDF - Supplemental Material
See Usage Policy.

41kB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170419-130606747

Abstract

The mechanism of catalytic hydroarylation of olefins by the homogeneous Ru(Tp)(CO)(Ph)(NCCH_3) catalyst recently reported by Gunnoe et al. is characterized using quantum mechanics (density functional theory). The catalytic cycle features two key steps, 1,2-olefin insertion and C−H activation via an unusual mechanism, oxidative hydrogen migration. We find that these two key steps are competitive and that improving the rate of one step is detrimental to the rate of the other. The Ru catalyst has better balance and consequently higher activity than the previously explored Ir-based system.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja038399pDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja038399pPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja038399pPublisherSupporting Information
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2004 American Chemical Society. Received 8 September 2003. Published online 18 December 2003. Published in print 1 January 2004. We wish to thank the Chevron Texaco Energy Research and Technology Co. for financial support, and Dr. Roy Periana for helpful discussions. The computer facilities of the MSC were provided by support from DURIP and MURI.
Funders:
Funding AgencyGrant Number
Chevron Texaco Energy Research and Technology Co.UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:2
DOI:10.1021/ja038399p
Record Number:CaltechAUTHORS:20170419-130606747
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170419-130606747
Official Citation:Mechanism of Ru(II)-Catalyzed Olefin Insertion and C−H Activation from Quantum Chemical Studies Jonas Oxgaard and William A. Goddard, III Journal of the American Chemical Society 2004 126 (2), 442-443 DOI: 10.1021/ja038399p
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76697
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Apr 2017 21:48
Last Modified:15 Nov 2021 17:02

Repository Staff Only: item control page