Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of [MnIV4O5(terpy)4(H2O)2](ClO4)6.
A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [[(H(2)O)(terpy)Mn(IV)(micro-O)(2)Mn(IV)(terpy)](2)(micro-O)](ClO(4))(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 [Mn(III/IV)(2)O(2)(terpy)(2)(OH(2))(2)](3+) to Mn(2+) and a Mn(IV/IV)(2)O(2)(terpy)(2) species; the latter complex slowly dimerizes to form the title complex. Protonation of a micro-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [Mn(III/)(IV)(2)O(2)(bpy)(4)](3+) system.
Chen
Hongyu
H
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Faller
J W
JW
Crabtree
Robert H
RH
Brudvig
Gary W
GW
D018360:Crystallography, X-Ray; D019281:Dimerization; D006863:Hydrogen-Ion Concentration; D008954:Models, Biological; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry* / Q000378:metabolism; D010100:Oxygen / Q000378:metabolism*; D045332:Photosystem II Protein Complex / Q000737:chemistry* / Q000378:metabolism*; D021241:Spectrometry, Mass, Electrospray Ionization; D013053:Spectrophotometry
C490328:(MnIV4O5(terpy)4(H2O)2)(ClO4)6; D009942:Organometallic Compounds; D045332:Photosystem II Protein Complex; D010100:Oxygen