Influence of ligand flexibility on the electronic structure of oxidized NiIII-phenoxide complexes

Minoru Kawai, Takahide Yamaguchi, Shigeyuki Masaoka, Fumito Tani, Takamitsu Kohzuma, Linus Chiang, Tim Storr, Kaoru Mieda, Takashi Ogura, Robert K. Szilagyi, Yuichi Shimazaki

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Abstract

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 NiIII salen-type complexes depends on the chelate ring size of the dinitrogen backbone.

Original languageEnglish
Pages (from-to)10195-10202
Number of pages8
JournalInorganic chemistry
Volume53
Issue number19
DOIs
Publication statusPublished - Oct 6 2014

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Kawai, M., Yamaguchi, T., Masaoka, S., Tani, F., Kohzuma, T., Chiang, L., ... Shimazaki, Y. (2014). Influence of ligand flexibility on the electronic structure of oxidized NiIII-phenoxide complexes. Inorganic chemistry, 53(19), 10195-10202. https://doi.org/10.1021/ic501181k