Oxygen‐Atom Transfer Chemistry and Thermolytic Properties of a Di‐tert‐Butylphosphate‐Ligated Mn4O4 Cubane |
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| Authors: | Kurt M. Van Allsburg Dr. Eitan Anzenberg Dr. Walter S. Drisdell Dr. Junko Yano Prof. T. Don Tilley |
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| Affiliation: | 1. Department of Chemistry, University of California, 420 Latimer Hall, Berkeley, CA 94720 (USA);2. Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory (USA);3. Materials Sciences Division, Lawrence Berkeley National Laboratory (USA);4. Physical Biosciences Division, Lawrence Berkeley National Laboratory (USA);5. Chemical Sciences Division, Lawrence Berkeley National Laboratory (USA) |
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| 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 MnII species. Finally, the related butterfly complex [Mn4O2{O2P(pin)}6(bpy)2] (pin=pinacolate) is described. |
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| Keywords: | artificial photosynthesis cubanes oxygen‐atom transfer thermolytic molecular precursor water oxidation |
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