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Heterolytic CH Activation with a Cyclometalated Platinum(II) 6-Phenyl-4,4‘-di-tert-butyl-2,2-Bipyridine Complex

Young, Kenneth J. H. and Meier, Steven K. and Gonzales, Jason M. and Oxgaard, Jonas and Goddard, William A., III and Periana, Roy A. (2006) Heterolytic CH Activation with a Cyclometalated Platinum(II) 6-Phenyl-4,4‘-di-tert-butyl-2,2-Bipyridine Complex. Organometallics, 25 (20). pp. 4734-4737. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20170725-150659069

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Abstract

The more electron-rich, thermally, air, and protic stable, cyclometalated Pt(II)(NNC) trifluoroacetate complex (3) (NNC = κ^3-6-phenyl-4,4‘-di-tert-butyl-2,2‘-bipyridine) was synthesized with the expectation that it would be less susceptible to H_2O inhibition than the Pt(bpym)(TFA)_2 system (bpym = κ^2-2,2‘-bipyrimidine) for the catalytic oxidation of hydrocarbons. Complex 3 was found to catalyze the H/D exchange between benzene and trifluoroacetic acid via CH activation but at a rate slower than the Pt(bpym) complex. Experimental and theoretical studies show that while the use of the more electron-rich NNC ligand motif lowered the ΔH for substrate coordination relative to the Pt(bpym) system, a larger increase in the barrier for CH cleavage led to an increase in the overall barrier for CH activation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om060410hDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om060410hPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om060410hPublisherSupporting Information
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Periana, Roy A.0000-0001-7838-257X
Additional Information:© 2006 American Chemical Society. Received 14 May 2006. Published online 24 August 2006. Published in print 1 September 2006. We thank Mohammad Yousufuddin for X-ray structure determinations. We thank Dr. W. C. Kaska, Vadim Ziatdinov, and Oleg Mironov for helpful discussions. The authors acknowledge the National Science Foundation (CHE-0328121), U.S. Department of Energy (DE-FC36-04GO14276), and ChevronTexaco Energy Technology Company for financial support for this research.
Funders:
Funding AgencyGrant Number
NSFCHE-0328121
Department of Energy (DOE)DE-FC36-04GO14276
ChevronTexaco Energy Technology CompanyUNSPECIFIED
Issue or Number:20
Record Number:CaltechAUTHORS:20170725-150659069
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170725-150659069
Official Citation:Heterolytic CH Activation with a Cyclometalated Platinum(II) 6-Phenyl-4,4‘-di-tert-butyl-2,2-Bipyridine Complex Kenneth J. H. Young, Steven K. Meier, Jason M. Gonzales, Jonas Oxgaard, William A. Goddard III, and Roy A. Periana Organometallics 2006 25 (20), 4734-4737 DOI: 10.1021/om060410h
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79351
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:25 Jul 2017 22:30
Last Modified:03 Oct 2019 18:19

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