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Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage

journal contribution
posted on 2023-05-17, 15:05 authored by Powers, DC, Lee, E, Alireza AriafardAlireza Ariafard, Sanford, MS, Brian YatesBrian Yates, Allan CantyAllan Canty, Ritter, T
Oxidation of binuclear Pd(II) complexes with PhICl2 or PhI(OAc)2 has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF3+") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with "CF3+" reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.

History

Publication title

Journal of the American Chemical Society

Volume

134

Issue

29

Pagination

12002-12009

ISSN

0002-7863

Department/School

School of Natural Sciences

Publisher

Amer Chemical Soc

Place of publication

1155 16Th St, Nw, Washington, USA, Dc, 20036

Rights statement

Copyright 2012 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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