Reversible Electrochemical Generation of a Rhodium(II) Porphyrin: Thwarting Disproportionation with Weakly Coordinating Anions

We report electrochemical generation of a stable Rh(II) porphyrin (RhII(F28TPP)) from a four-coordinate Rh(I) precursor [RhI(F28TPP)]dissolved in weakly coordinating electrolyte solutions. This work provides the first example of an unambiguously reversible one-electron electrochemical oxidation of a RhI(por), and demonstrates that electrochemical oxidation can be performed under conditions that are compatible with alkane activation. These studies begin to classify those media capable of supporting a stable RhII(por), and those that induce disproportionation.