Oxidation of binuclear Pd(II) complexes with PhICl<sub>2</sub> or
PhI(OAc)<sub>2</sub> 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<sub>3</sub><sup>+</sup>”) 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<sub>3</sub><sup>+</sup>” 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