Oxygen-atom transfer chemistry and thermolytic properties of a di-tert-butylphosphate-ligated Mn4O4 cubane.

Autor: Van Allsburg KM; 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)., Anzenberg E, Drisdell WS, Yano J, Tilley TD
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2015 Mar 16; Vol. 21 (12), pp. 4646-54. Date of Electronic Publication: 2015 Feb 11.
DOI: 10.1002/chem.201406114
Abstrakt: [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.
(© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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