Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of MnIV4O5(terpy) 4(H2O)2](CIO4)6

Hongyu Chen, J. W. Faller, Robert H. Crabtree, Gary W. Brudvig

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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)](CIO4) 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/IV 2O2(terpy)2(OH2)2] 3+ to Mn2+ and a MnIV/IV2O 2(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 [Mn III/IV2O2(bpy)4]3+ system.

Original languageEnglish
Pages (from-to)7345-7349
Number of pages5
JournalJournal of the American Chemical Society
Volume126
Issue number23
DOIs
Publication statusPublished - Jun 16 2004

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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