Reversible electrochemical generation of a rhodium(II) porphyrin: thwarting disproportionation with weakly coordinating anions.

We report electrochemical generation of a stable Rh(II) porphyrin (Rh(II)(F(28)TPP)) from a four-coordinate Rh(I) precursor [Rh(I)(F(28)TPP)](-) dissolved in weakly coordinating electrolyte solutions. This work provides the first example of an unambiguously reversible one-electron electrochemical oxidation of a Rh(I)(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 Rh(II)(por), and those that induce disproportionation.