Toward synthetic models for high oxidation state forms of the Photosystem II active site metal cluster: the first tetranuclear manganese cluster containing a [Mn4(μ-O)5]6+ core†,10.1039/B111554E

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Toward synthetic models for high oxidation state forms of the Photosystem II active site metal cluster: the first tetranuclear manganese cluster containing a [Mn4(μ-O)5]6+ core†

Sumitra Mukhopadhyay,Richard J. Staples,William H. Armstrong

Chemical Communications Pub Date : 03/21/2002 00:00:00 , DOI:10.1039/B111554E

Abstract

The first tetrameric high valent manganese complex consisting of a Mn^IV₄(μ-O)₅ bridged core, [Mn₄(μ-O)₅(dmb)₄(dmbO)₂](ClO₄)₄, was isolated via dimanganese (III,IV) and (IV,IV) intermediates in presence of the oxidant tert-butyl hydroperoxide and was characterized by X-ray crystallography, electrochemistry, infrared, UV-visible, ¹H NMR, and mass spectroscopy; the structure found differs greatly from a proposal for the putative Mn₄O₅aggregate found in Photosystem II.