title: Manganese-Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts.
abstract: Incorporation of Mn into an established water oxidation catalyst based on a Co(III)4O4cubane 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 [MnIVCoIII3]. 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 MnCo3O4cubane 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.
authors.affiliation: Department of Chemistry, University of California at Berkeley , Berkeley, California 94720-1460, United States.
authors.forename: Andy I
authors.identifier: 0000-0003-4137-6453
authors.initials: AI
authors.lastname: Nguyen
authors.affiliation: Department of Chemistry, University of California at Davis , Davis, California 95616, United States.
authors.forename: Daniel L M
authors.initials: DLM
authors.lastname: Suess
authors.affiliation: Department of Chemistry, University of California at Berkeley , Berkeley, California 94720-1460, United States.
authors.forename: Lucy E
authors.initials: LE
authors.lastname: Darago
authors.affiliation: Department of Chemistry, University of California at Davis , Davis, California 95616, United States.
authors.forename: Paul H
authors.initials: PH
authors.lastname: Oyala
authors.affiliation: Department of Chemistry, University of California at Berkeley , Berkeley, California 94720-1460, United States.
authors.forename: Daniel S
authors.identifier: 0000-0001-8921-3659
authors.initials: DS
authors.lastname: Levine
authors.affiliation: Department of Chemistry, University of California at Berkeley , Berkeley, California 94720-1460, United States.
authors.forename: Micah S
authors.identifier: 0000-0002-8549-506X
authors.initials: MS
authors.lastname: Ziegler
authors.affiliation: Department of Chemistry, University of California at Davis , Davis, California 95616, United States.
authors.forename: R David
authors.initials: RD
authors.lastname: Britt
authors.affiliation: Department of Chemistry, University of California at Berkeley , Berkeley, California 94720-1460, United States.
authors.forename: T Don
authors.initials: TD
authors.lastname: Tilley
mesh_terms: D002384:Catalysis; D003035:Cobalt / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D010087:Oxides; D014867:Water; D003035:Cobalt; D008345:Manganese