Dimer-of-dimers model for the oxygen-evolving complex of photosystem II.: synthesis and properties of [MnIV4O5(terpy)4(H2O)2](ClO4)6
Dimer-of-dimers model for the oxygen-evolving complex of photosystem II.: synthesis and properties of [MnIV4O5(terpy)4(H2O)2](ClO4)6
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DOI：
10.1021/ja037389l
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发表时间：
2004-06-16
影响因子：
15
通讯作者：
Brudvig, GW
中科院分区：
文献类型：
--
作者：
Chen, HY;Faller, JW;Brudvig, GW
合成了光系统II放氧复合物的二聚体模型化合物[{（H_2O）-（terpy）Mn-IV（mu-O）（2）Mn-IV（terpy）}（2）（mu-O）]（ClO_4）（6）（terpy = 2，2 '：6'，2”-三联吡啶），并通过X-射线晶体学和ESI-MS进行了表征。发现低pH促进[（Mn_2 O_2）-O-III/IV（terpy）（2）（OH_2）（2）]（3+）向Mn ~（2+）和（Mn_2 O_2）-O-IV/IV（terpy）（2）物种的转化;后者复合物缓慢二聚形成标题复合物。基于与[（Mn_2O_2）-O-III/IV（bpy）（4）]（3+）体系的类比，提出了μ-氧桥的质子化是引发该反应的关键。
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.