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.
Mukhopadhyay
Sumitra
S
Department of Chemistry, Eugene F. Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Mok
Henry J
HJ
Staples
Richard J
RJ
Armstrong
William H
WH
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