Influence of Ligand Flexibility on the Electronic Structure of Oxidized NiIII-Phenoxide Complexes

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• 作者：Minoru Kawai ; Takahide Yamaguchi ; Shigeyuki Masaoka ; Fumito Tani ; Takamitsu Kohzuma ; Linus Chiang ; Tim Storr ; Kaoru Mieda ; Takashi Ogura ; Robert K. Szilagyi ; Yuichi Shimazaki
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：October 6, 2014
• 年：2014
• 卷：53
• 期：19
• 页码：10195-10202
• 全文大小：462K
• ISSN：1520-510X

文摘

One-electron-oxidized Ni^III-phenoxide complexes with salen-type ligands, [Ni(salen)py₂]²⁺ ([1^en-py]²⁺) and [Ni(1,2-salcn)py₂]²⁺ ([1^cn-py]²⁺), with a five-membered chelate dinitrogen backbone and [Ni(salpn)py₂]²⁺ ([2^pn-py]²⁺), with a six-membered chelate backbone, have been characterized with a combination of experimental and theoretical methods. The five-membered chelate complexes [1^en-py]²⁺ and [1^cn-py]²⁺ were assigned as Ni^III-phenoxyl radical species, while the six-membered chelate complex [2^pn-py]²⁺ was concluded to be a Ni^II-bis(phenoxyl radical) species with metal-centered reduction in the course of the one-electron oxidation of the Ni^III-phenoxide complex [2^pn-py]⁺. Thus, the oxidation state of the one-electron-oxidized Ni^III salen-type complexes depends on the chelate ring size of the dinitrogen backbone.