Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts

Incorporation of Mn into an established water oxidation catalyst based on a Co(III)₄O₄ cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo₃O₄(OAc)₅py₃ (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc^- ligand for Cl^- (1-Cl), NO₃^- (1-NO₃), and pyridine ([1-py]⁺). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [Mn^IVCo^III₃]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo₃O₄ cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.