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

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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:

URL	URL Type	Description
http://dx.doi.org/10.1021/ja038399p	DOI	Article
http://pubs.acs.org/doi/abs/10.1021/ja038399p	Publisher	Article
http://pubs.acs.org/doi/suppl/10.1021/ja038399p	Publisher	Supporting Information

ORCID:

Author	ORCID
Goddard, William A., III	0000-0003-0097-5716

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 Agency	Grant Number
Chevron Texaco Energy Research and Technology Co.	UNSPECIFIED
Army Research Office (ARO)	UNSPECIFIED
Office of Naval Research (ONR)	UNSPECIFIED

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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

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ID Code:

76697

Collection:

CaltechAUTHORS

Deposited By:

Ruth Sustaita

Deposited On:

19 Apr 2017 21:48

Last Modified:

15 Nov 2021 17:02

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