Dimer-of-Dimers Model for the Oxygen-Evolving Complex of Photosystem II. Synthesis and Properties of [MnIV4O5(terpy)4(H2O)2](ClO4)6
- 19 May 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (23), 7345-7349
- https://doi.org/10.1021/ja037389l
Abstract
A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [{(H2O)(terpy)MnIV(μ-O)2MnIV(terpy)}2(μ-O)](ClO4)6 (terpy = 2,2‘:6‘,2‘ ‘-terpyridine), has been prepared and characterized by X-ray crystallography and ESI-MS. Low pH was found to promote the disproportionation of [MnIII/IV2O2(terpy)2(OH2)2]3+ to Mn2+ and a MnIV/IV2O2(terpy)2 species; the latter complex slowly dimerizes to form the title complex. Protonation of a μ-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [MnIII/IV2O2(bpy)4]3+ system.Keywords
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