Influence of ligand flexibility on the electronic structure of oxidized Ni(III)-phenoxide complexes
Influence of ligand flexibility on the electronic structure of oxidized Ni(III)-phenoxide complexes
复制标题
配体柔性对氧化镍(III)-苯氧基配合物电子结构的影响
DOI：
10.1021/ic501181k
复制
发表时间：
2014
影响因子：
4.6
通讯作者：
and Y. Shimazaki
中科院分区：
文献类型：
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作者：
M. Kawai;T. Yamaguchi;S. Masaoka;F. Tani;T. Kohzuma;L. Chiang;T. Storr;K. Mieda;T. Ogura;r. K. Szilagyi;and Y. Shimazaki
用实验和理论相结合的方法表征了六元络合骨架的Salen型配体[Ni(Salen)py2]2+([1en-py]2+)和[Ni(1，2-salcn)py2]2+([1cn-py]2+)和[Ni(Salpn)py2]2+([2pn-py]2+)的单电子氧化NiIII-苯氧化物配合物.五元配合物[1en-py]2+和[1cn-py]2+被归属为NiIII-苯氧基自由基物种，而六元配合物[2pn-py]2+在NiIII-苯氧基配合物[2pn-py]+的单电子氧化过程中是以金属为中心还原的NiII-双(苯氧基)自由基物种。因此，单电子氧化的NiIIIsalen型络合物的氧化状态取决于二氮主链的螯合环大小。
One-electron-oxidized NiIII-phenoxide complexes with salen-type ligands, [Ni(salen)py2]2+([1en-py]2+) and [Ni(1,2-salcn)py2]2+([1cn-py]2+), with a five-membered chelate dinitrogen backbone and [Ni(salpn)py2]2+([2pn-py]2+), with a six-membered chelate backbone, have been characterized with a combination of experimental and theoretical methods. The five-membered chelate complexes[1en-py]2+and[1cn-py]2+were assigned as NiIII-phenoxyl radical species, while the six-membered chelate complex[2pn-py]2+was concluded to be a NiII-bis(phenoxyl radical) species with metal-centered reduction in the course of the one-electron oxidation of the NiIII-phenoxide complex[2pn-py]+. Thus, the oxidation state of the one-electron-oxidized NiIIIsalen-type complexes depends on the chelate ring size of the dinitrogen backbone.