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Oxygen‐Atom Transfer Chemistry and Thermolytic Properties of a Di‐ tert ‐Butylphosphate‐Ligated Mn 4 O 4 Cubane
Author(s) -
Van Allsburg Kurt M.,
Anzenberg Eitan,
Drisdell Walter S.,
Yano Junko,
Tilley T. Don
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406114
Subject(s) - cubane , chemistry , metaphosphate , manganese , oxygen , photosystem ii , crystallography , pyrophosphate , acceptor , photochemistry , crystal structure , photosynthesis , phosphate , organic chemistry , biochemistry , enzyme , physics , condensed matter physics
[Mn 4 O 4 {O 2 P(O t Bu) 2 } 6 ] ( 1 ), an Mn 4 O 4 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 (PEt 3 ), to give the butterfly complex [Mn 4 O 2 {O 2 P(O t Bu) 2 } 6 (OPEt 3 ) 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 Mn 4 O 4 unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to Mn II species. Finally, the related butterfly complex [Mn 4 O 2 {O 2 P(pin)} 6 (bpy) 2 ] (pin=pinacolate) is described.