title: Oxygen-atom transfer chemistry and thermolytic properties of a di-tert-butylphosphate-ligated Mn4O4 cubane.
abstract: [Mn4O4{O2P(OtBu)2}6] (1), an Mn4O4 cubane complex combining the structural inspiration of the photosystem II oxygen-evolving complex with thermolytic precursor ligands, was synthesized and fully characterized. Core oxygen atoms within complex 1 are transferred upon reaction with an oxygen-atom acceptor (PEt3), to give the butterfly complex [Mn4O2{O2P(OtBu)2}6(OPEt3)2]. The cubane structure is restored by reaction of the latter complex with the O-atom donor PhIO. Complex 1 was investigated as a precursor to inorganic Mn metaphosphate/pyrophosphate materials, which were studied by X-ray absorption spectroscopy to determine the fate of the Mn4O4 unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to Mn(II) species. Finally, the related butterfly complex [Mn4O2{O2P(pin)}6(bpy)2] (pin = pinacolate) is described.
authors: Department of Chemistry, University of California, 420 Latimer Hall, Berkeley, CA 94720 (USA); Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory (USA); Materials Sciences Division, Lawrence Berkeley National Laboratory (USA).
authors: Kurt M
authors: KM
authors: Van Allsburg
authors: Eitan
authors: E
authors: Anzenberg
authors: Walter S
authors: WS
authors: Drisdell
authors: Junko
authors: J
authors: Yano
authors: T Don
authors: TD
authors: Tilley
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D008024:Ligands; D008345:Manganese / Q000737:chemistry; D008968:Molecular Conformation; D010755:Organophosphates / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D045332:Photosystem II Protein Complex / Q000737:chemistry; D013816:Thermodynamics; D014867:Water / Q000737:chemistry; D056928:X-Ray Absorption Spectroscopy
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D010755:Organophosphates; D045332:Photosystem II Protein Complex; D014867:Water; C071068:tert-butyl phosphate; D008345:Manganese; D010100:Oxygen
keywords: artificial photosynthesis; cubanes; oxygen-atom transfer; thermolytic molecular precursor; water oxidation