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Oxygen-atom transfer chemistry and thermolytic properties of a Di-tert-butylphosphate-ligated Mn4O4cubane

  • Author(s): Van Allsburg, KM
  • Anzenberg, E
  • Drisdell, WS
  • Yano, J
  • Tilley, TD
  • et al.

Published Web Location

https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201406114
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Abstract

©2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. [Mn4O4{O2P(OtBu)2}6] (1), an Mn4O4cubane 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 Oatom 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 Mn4O4unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to MnIIspecies. Finally, the related butterfly complex [Mn4O2{O2P(pin)}6(bpy)2] ( pin = pinacolate) is described.

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