Publication: Connecting Binuclear Pd(III) and Mononuclear Pd(IV) Chemistry by Pd–Pd Bond Cleavage
Date
2012
Published Version
Journal Title
Journal ISSN
Volume Title
Publisher
American Chemical Society
The Harvard community has made this article openly available. Please share how this access benefits you.
Citation
Powers, David C., Eunsung Lee, Alireza Ariafard, Melanie S. Sanford, Brian F. Yates, Allan J. Canty, and Tobias Ritter. 2012. Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd–Pd bond cleavage. Journal of the American Chemical Society 134 (29): 12002-12009
Research Data
Abstract
Oxidation of binuclear Pd(II) complexes with PhICl\(_2\) 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 (“CF\(_3^+\)”) 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 “CF\(_3^+\)” 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.
Description
Other Available Sources
Keywords
forming reductive elimination, effective core potentials, bidentate nitrogen ligands, C-H activation, palladium(IV) complexes, oxidative addition, basis-sets, electrophilic trifluoromethylation, molecular calculations, polarization functions
Terms of Use
This article is made available under the terms and conditions applicable to Open Access Policy Articles (OAP), as set forth at Terms of Service