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Published October 13, 2010 | Accepted Version + Supplemental Material
Journal Article Open

Bimetallic Reductive Elimination from Dinuclear Pd(III) Complexes

Abstract

In 2009, we reported C-halogen reductive elimination reactions from dinuclear Pd(III) complexes and implicated dinuclear intermediates in Pd(OAc)2-catalyzed C-H oxidation chemistry. Herein, we report results of a thorough experimental and theoretical investigation of the mechanism of reductive elimination from such dinuclear Pd(III) complexes, which establish the role of each metal during reductive elimination. Our results implicate reductive elimination from a complex in which the dinuclear core is intact and suggest that redox synergy between the two metals is responsible for the facile reductive elimination reactions observed.

Additional Information

© 2010 American Chemical Society. Received April 29, 2010; Published In Issue October 13, 2010; Article ASAP September 21, 2010. We thank Douglas M. Ho, Jessica Y. Wu, and Takeru Furuya for X-ray crystallographic analysis, Robert Nielsen and David Ford for insightful discussions, Sanofi Aventis for a graduate fellowship for D.C.P., the reviewers of this manuscript for comments, which improved the quality of the manuscript, and the NSF (CHE-0952753) and NIH-NIGMS (GM088237) for funding. Computational facilities were funded by grants from ARO-DURIP and ONR-DURIP.

Attached Files

Accepted Version - nihms238678.pdf

Supplemental Material - ja1036644_si_001.pdf

Supplemental Material - ja1036644_si_002.cif

Supplemental Material - ja1036644_si_003.cif

Supplemental Material - ja1036644_si_004.cif

Supplemental Material - ja1036644_si_005.cif

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