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Hydrogen tunneling in protonolysis of platinum(II) and palladium(II) methyl complexes: mechanistic implications

Bercaw, John E. and Chen, George S. and Labinger, Jay A. and Lin, Bo-Lin (2008) Hydrogen tunneling in protonolysis of platinum(II) and palladium(II) methyl complexes: mechanistic implications. Journal of the American Chemical Society, 130 (52). pp. 17654-17655. ISSN 0002-7863. doi:10.1021/ja807427d.

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The selective transformation of C-H bonds is an important area of current research; over the past several decades, numerous examples of C-H activation by transition metals have appeared in the literature.1 Of particular significance is the development of a number of homogeneous catalytic systems based on late transition metals, especially platinum2 and palladium.3 Several general mechanisms for C-H activation by transition metal complexes have been identified, including (1) electrophilic activation, (2) oxidative addition, (3) σ-bond metathesis, (4) 1,2-addition to metal-ligand multiple bonds, (5) H-atom abstraction by metal-oxo complexes, and (6) metalloradical activation.4 Kinetic hydrogen/deuterium isotope effects (KIEs) have been used extensively by many groups to probe the nature of these reactions and to gain key mechanistic insights.5

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Labinger, Jay A.0000-0002-1942-9232
Additional Information:Received September 25, 2008. Published on Web 12/04/2008. This work was supported by BP through the MC2 program. An NSF Graduate Research Fellowship to GSC is gratefully acknowledged. We thank Drs. Michael W. Day and Lawrence M. Henling for assistance with X-ray crystallography and Dr. Jonathan S. Owen for suggestions in the preparation of complex 1b. Supporting Information Available: Detailed experimental data. This material is available free of charge via the Internet at
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Issue or Number:52
Record Number:CaltechAUTHORS:20090724-092407360
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:14659
Deposited By: Ruth Sustaita
Deposited On:10 Aug 2009 15:54
Last Modified:08 Nov 2021 23:13

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