Possible mechanisms for the O-O bond formation in oxygen evolution reaction at the CaMn4O5(H2O)4 cluster of PSII refined to 1.9 Å X-ray resolution
Possible mechanisms for the O-O bond formation in oxygen evolution reaction at the CaMn4O5(H2O)4 cluster of PSII refined to 1.9 Å X-ray resolution
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DOI：
10.1016/j.cplett.2011.06.021
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发表时间：
2011-07-26
影响因子：
2.8
通讯作者：
Yamaguchi, K.
中科院分区：
文献类型：
--
作者：
Yamanaka, S.;Isobe, H.;Yamaguchi, K.
最近，Umena 等人。确定了光系统 II (PSII) 的析氧络合物 (OEC) 中 CaMn4O5 簇 (1) 的 X 射线衍射 (XRD) 结构，分辨率精化至 1.9 埃。使用该 XRD 结构对 1 进行 UB3LYP 计算，以阐明 PSII 析氧反应中氧-氧 (O-O) 键形成的可能机制。所得溶液用于自然轨道（NO）分析，以获得不稳定化学键的LUMO，这清楚地表明了氢氧化物（或水分子）对1的亲电O（56）和/或O（57）位点进行亲核攻击的可能性。（C）2011 Elsevier B.V。保留所有权利。
Very recently Umena et al. have determined the X-ray diffraction (XRD) structure of the CaMn4O5 cluster (1) in the oxygen-evolving complex (OEC) of photosystem II (PSII) refined to 1.9 angstrom resolution. UB3LYP calculations of 1 using this XRD structure were performed to elucidate possible mechanisms for the oxygen-oxygen (O-O) bond formation in oxygen evolution reaction of PSII. The solutions obtained were used for natural orbital (NO) analysis to obtain LUMOs of labile chemical bonds, which clearly indicated the possibilities of nucleophilic attack of hydroxide (or water molecule) to the electrophilic O(56) and/ or O(57) sites of 1. (C) 2011 Elsevier B. V. All rights reserved.