Heterolytic CH Activation and Catalysis by an O-Donor Iridium−Hydroxo Complex

Tenn, William J., III and Young, Kenneth J. H. and Oxgaard, Jonas and Nielsen, Robert J. and Goddard, William A., III and Periana, Roy A. (2006) Heterolytic CH Activation and Catalysis by an O-Donor Iridium−Hydroxo Complex. Organometallics, 25 (21). pp. 5173-5175. ISSN 0276-7333. doi:10.1021/om060657e. https://resolver.caltech.edu/CaltechAUTHORS:20170725-105419764

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Abstract

A well-defined, O-donor ligated iridium hydroxide complex is reported that is competent for benzene CH activation and long-lived catalytic H/D exchange between benzene and water. An inverse dependence of the H/D exchange rate on added pyridine, a kinetic isotope effect (KIE) of 2.65 ± 0.56 for CH activation with 1,3,5-trideuteriobenzene, a KIE of 1.07 ± 0.24 with C_6H_6/C_6D_6, and DFT calculations are consistent with the CH activation proceeding via rate-determining benzene coordination followed by fast CH cleavage via a σ-bond-metathesis transition state.

Item Type:

Article

Related URLs:

URL	URL Type	Description
http://dx.doi.org/10.1021/om060657e	DOI	Article
http://pubs.acs.org/doi/abs/10.1021/om060657e	Publisher	Article
http://pubs.acs.org/doi/suppl/10.1021/om060657e	Publisher	Supporting Information

ORCID:

Author	ORCID
Nielsen, Robert J.	0000-0002-7962-0186
Goddard, William A., III	0000-0003-0097-5716
Periana, Roy A.	0000-0001-7838-257X

Additional Information:

© 2006 American Chemical Society. Received 21 July 2006. Published online 2 September 2006. Published in print 1 October 2006. We acknowledge Dr. M. Yousufuddin and Prof. Robert Bau for solving the crystal structure of 1 and Vadim R. Ziatdinov for helpful discussions. We thank the National Science Foundation (Grant No. CHE-0328121) and Chevron Energy Research & Technology Co. for financial support for this research.

Funders:

Funding Agency	Grant Number
NSF	CHE-0328121
Chevron Energy Research & Technology Co.	UNSPECIFIED

Issue or Number:

DOI:

10.1021/om060657e

Record Number:

CaltechAUTHORS:20170725-105419764

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20170725-105419764

Official Citation:

Heterolytic CH Activation and Catalysis by an O-Donor Iridium−Hydroxo Complex William J. Tenn, III, Kenneth J. H. Young, Jonas Oxgaard, Robert J. Nielsen, William A. Goddard, III, and Roy A. Periana Organometallics 2006 25 (21), 5173-5175 DOI: 10.1021/om060657e

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ID Code:

79334

Collection:

CaltechAUTHORS

Deposited By:

Ruth Sustaita

Deposited On:

25 Jul 2017 18:05

Last Modified:

15 Nov 2021 17:47

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