Shape-shifting tetranuclear oxo-bridged manganese cluster: relevance to photosystem II water oxidase active site.
The redox properties of the "dimer-of-dimers" complex, [{Mn2(mu-O)2(tphpn)}2]4+ (1) (where Htphpn = N,N,N',N'-tetra(2-methylpyridyl)-2-hydroxypropane-diamine) were investigated. The structure changes dramatically to an adamantane-shaped core upon one-electron oxidation. On the other hand, the one-electron reduced product of 1, [Mn4O4(tphpn)2]3+, exhibits a hyperfine-structured multiline EPR signal very similar to the so-called S0 state of the tetramanganese cluster, which resides at the Photosystem II water oxidase active site.
Department of Chemistry, Eugene F. Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Sumitra
S
Mukhopadhyay
Henry J
HJ
Mok
Richard J
RJ
Staples
William H
WH
Armstrong
D001665:Binding Sites; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D007700:Kinetics; D008345:Manganese / Q000737:chemistry*; D010088:Oxidoreductases / Q000737:chemistry* / Q000378:metabolism; D045332:Photosystem II Protein Complex / Q000737:chemistry*; D014867:Water / Q000737:chemistry* / Q000378:metabolism
D045332:Photosystem II Protein Complex; D014867:Water; D008345:Manganese; D010088:Oxidoreductases