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C-H Bond Activation by [{(Diimine)Pd(μ-OH)}2]2+ Dimers: Mechanism-Guided Catalytic Improvement

Bercaw, John E. and Hazari, Nilay and Labinger, Jay A. and Oblad, Paul E. (2008) C-H Bond Activation by [{(Diimine)Pd(μ-OH)}2]2+ Dimers: Mechanism-Guided Catalytic Improvement. Angewandte Chemie International Edition, 47 (51). pp. 9941-9943. ISSN 1433-7851. http://resolver.caltech.edu/CaltechAUTHORS:BERacie08

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Abstract

These conclusions—that the hydroxy-bridged dimer 1b is the most reactive species in the Pd system, considerably more reactive than either 2a or 2b towards C-H bond activation, and that there is an important solvent-assisted component in the rate law—suggest a way to substantially improve the catalytic conversion of cyclohexene into benzene [Eq. (3)]. Our previous studies involved 2b (or mixtures of 1b and 2b) in the noncoordinating solvent dichloroethane. In a typical experiment, after 24 h under 1 atm of O2 with 5 mol% of 2b as the catalyst, 8% of the cyclohexene had been converted into benzene; furthermore, there was an initiation period before any reaction occurred, and competing disproportionation of cyclohexene to benzene and cyclohexane was a major side reaction.[3] In contrast, under the same conditions but using only 1 mol% of pure 1b as the catalyst and TFE as solvent, conversion was 25% after 24 h, with no induction period or competing isomerization.[7]


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/anie.200804455DOIArticle
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2008 Wiley-VCH. Received: September 10, 2008. Published online: November 12, 2008. This work was supported by BP through the MC2 program, and Caltech through a Switzer fellowship to P.F.O. We thank Larry Henling and Michael Day for assistance with crystallography.
Funders:
Funding AgencyGrant Number
BP MC2 programUNSPECIFIED
Robert and Patricia Switzer FoundationUNSPECIFIED
Subject Keywords:C-H activation; homogeneous catalysis; kinetics; oxidation; palladium
Record Number:CaltechAUTHORS:BERacie08
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:BERacie08
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13070
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:16 Jan 2009 19:19
Last Modified:21 Sep 2017 21:46

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