Toward models for the full oxygen-evolving complex of photosystem II by ligand coordination to lower the symmetry of the Mn3CaO4 cubane: demonstration that electronic effects facilitate binding of a fifth metal.
Toward models for the full oxygen-evolving complex of photosystem II by ligand coordination to lower the symmetry of the Mn3CaO4 cubane: demonstration that electronic effects facilitate binding of a fifth metal.
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DOI：
10.1021/ja508160x
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发表时间：
2014-10-15
影响因子：
15
通讯作者：
Agapie, Theodor
中科院分区：
文献类型：
--
作者：
Kanady, Jacob S.;Lin, Po-Heng;Carsch, Kurtis M.;Nielsen, Robert J.;Takase, Michael K.;Goddard, William A., III;Agapie, Theodor
合成的模型化合物已针对基准和更好地了解光系统II，一个低对称性Mn 4CaOn簇的放氧复合物（OEC）的电子结构，几何形状，光谱和反应性。在这里，低对称性MnIV 3GdO 4和MnIV 3CaO 4立方烷合成在一个合理的，逐步的方式，通过去对称化配体取代，造成显着的立方烷扭曲。由于增加的电子丰度和去对称化，Mn 3CaO 4单元的特定μ3-氧代部分变得更碱性，允许选择性质子化。第五个金属离子，Ag+，到同一网站的协调给出了Mn 3CaAgO 4簇模型的OEC的拓扑结构，通过显示一个立方烷基序和一个“悬垂”过渡金属。目前的合成策略提供了一个合理的路线图，以获得更准确的模型的生物催化剂。
Synthetic model compounds have been targeted to benchmark and better understand the electronic structure, geometry, spectroscopy, and reactivity of the oxygen-evolving complex (OEC) of photosystem II, a low-symmetry Mn4CaOn cluster. Herein, low-symmetry MnIV3GdO4 and MnIV3CaO4 cubanes are synthesized in a rational, stepwise fashion through desymmetrization by ligand substitution, causing significant cubane distortions. As a result of increased electron richness and desymmetrization, a specific μ3-oxo moiety of the Mn3CaO4 unit becomes more basic allowing for selective protonation. Coordination of a fifth metal ion, Ag+, to the same site gives a Mn3CaAgO4 cluster that models the topology of the OEC by displaying both a cubane motif and a “dangler” transition metal. The present synthetic strategy provides a rational roadmap for accessing more accurate models of the biological catalyst.
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影响因子：
21.8
作者：
Tsui EY;Tran R;Yano J;Agapie T
通讯作者：
Agapie T
影响因子：
15
作者：
Aromí, G;Wemple, MW;Christou, G
通讯作者：
Christou, G
影响因子：
15
作者：
Campbell, KA;Force, DA;Britt, RD
通讯作者：
Britt, RD
影响因子：
4.6
作者：
Glatzel P;Schroeder H;Pushkar Y;Boron T 3rd;Mukherjee S;Christou G;Pecoraro VL;Messinger J;Yachandra VK;Bergmann U;Yano J
通讯作者：
Yano J
影响因子：
15
作者：
Herbert DE;Lionetti D;Rittle J;Agapie T
通讯作者：
Agapie T