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. 2009 Nov 4;131(43):15618-20.
doi: 10.1021/ja905816q.

Oxidatively induced reductive elimination from ((t)Bu2bpy)Pd(Me)2: palladium(IV) intermediates in a one-electron oxidation reaction

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Oxidatively induced reductive elimination from ((t)Bu2bpy)Pd(Me)2: palladium(IV) intermediates in a one-electron oxidation reaction

Michael P Lanci et al. J Am Chem Soc. .

Abstract

This communication describes studies of oxidatively induced C-C bond-forming reductive elimination from ((t)Bu(2)bpy)Pd(II)(Me)(2). With the outer-sphere oxidant ferrocenium, the data are consistent with a mechanism involving Pd(III) and Pd(IV) intermediates, with C-C bond formation occurring from the latter. The reaction with Ag(+) appears to proceed via a Pd-Ag(+) adduct, which then undergoes inner sphere electron transfer to generate Pd(III). In contrast, the slower benzoquinone reaction forms ethane by a different pathway that does not involve methyl group scrambling and generates Pd(0) products.

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