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


Powers, DC and Lee, E and Ariafard, A and Sanford, MS and Yates, BF and Canty, AJ and Ritter, T, Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage, Journal of the American Chemical Society, 134, (29) pp. 12002-12009. ISSN 0002-7863 (2012) [Refereed Article]

Copyright Statement

Copyright 2012 American Chemical Society

DOI: doi:10.1021/ja304401u


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.

Item Details

Item Type:Refereed Article
Keywords:bond cleavages, bond-forming reactions, computational studies, nuclearity
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Yates, BF (Professor Brian Yates)
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:81599
Year Published:2012
Web of Science® Times Cited:133
Deposited By:Chemistry
Deposited On:2012-12-18
Last Modified:2017-10-25

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