Electrochemistry and Spectroscopy of Sulfate Complexes of (Tetraphenylporphyrinato)manganese

The electrochemical and spectroscopic properties of [Mn₂(tpp)₂(SO₄)] (H₂tpp=tetraphenylporphyrin=5,10,15,20‐tetraphenyl‐21H,23H‐porphine) were studied to characterize the stability of this compound as a function of solvent, redox state, and sulfate concentration. In non‐coordinating solvents such as 1,2‐dichloroethane, the dimer was stable, and two cyclic voltammetric waves were observed in the region for Mn^III reduction. These waves correspond to reduction of the dimer to [Mn^II(tpp)] and [Mn^III(tpp)(OSO₃)]^?, and reduction of [Mn^III(tpp)(OSO₃)]^? to [Mn^II(tpp)(OSO₃)]^2?, respectively. In the coordinating solvent DMSO, [Mn₂(tpp)₂(SO₄)] was unstable and dissociated to form [Mn^III(tpp)(DMSO)₂]⁺. A single voltammetric wave was observed for Mn^III reduction in this solvent, corresponding to formation of [Mn^II(tpp)(DMSO)]. In non‐coordinating solvent systems, addition of sulfate (as the bis(triphenylphosphoranylidene)ammonium (PPN⁺) salt) resulted in dimer dissociation, yielding [Mn^III(tpp)(OSO₃)]^?. Reduction of this monomer produced [Mn^II(tpp)(OSO₃)]^2?. In DMSO, addition of SO led to displacement of solvent molecules forming [Mn^III(tpp)(OSO₃)]^?. Reduction of this species in DMSO led to [Mn^II(tpp)(DMSO)].