Dimer-of-dimers model for the oxygen-evolving complex of photosystem II.: synthesis and properties of [MnIV4O5(terpy)4(H2O)2](ClO4)6

被引：124

作者：

Chen, HY ^{[1
]}

Faller, JW ^{[1
]}

Crabtree, RH ^{[1
]}

Brudvig, GW ^{[1
]}

机构：

[1] Yale Univ, Dept Chem, New Haven, CT 06520 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 23期

关键词：

D O I：

10.1021/ja037389l

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [{(H2O)-(terpy)Mn-IV(mu-O)(2)Mn-IV(terpy)}(2)(mu-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 [(Mn2O2)-O-III/IV(terpy)(2)(OH2)(2)](3+) to Mn2+ and a (Mn2O2)-O-IV/IV(terpy)(2) species; the latter complex slowly dimerizes to form the title complex. Protonation of a mu-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [(Mn2O2)-O-III/IV(bpy)(4)](3+) system.

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页码：7345 / 7349

页数：5

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