title: Influence of ligand flexibility on the electronic structure of oxidized Ni(III)-phenoxide complexes.
abstract: 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.
authors.affiliation: College of Science and ‡Graduate School of Science and Engineering, Ibaraki University , Bunkyo, Mito 310-8512, Japan.
authors.forename: Minoru
authors.initials: M
authors.lastname: Kawai
authors.forename: Takahide
authors.initials: T
authors.lastname: Yamaguchi
authors.forename: Shigeyuki
authors.initials: S
authors.lastname: Masaoka
authors.forename: Fumito
authors.initials: F
authors.lastname: Tani
authors.forename: Takamitsu
authors.initials: T
authors.lastname: Kohzuma
authors.forename: Linus
authors.initials: L
authors.lastname: Chiang
authors.forename: Tim
authors.initials: T
authors.lastname: Storr
authors.forename: Kaoru
authors.initials: K
authors.lastname: Mieda
authors.forename: Takashi
authors.initials: T
authors.lastname: Ogura
authors.forename: Robert K
authors.initials: RK
authors.lastname: Szilagyi
authors.forename: Yuichi
authors.initials: Y
authors.lastname: Shimazaki
mesh_terms: D004583:Electrons; D008024:Ligands; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D010087:Oxides; D009532:Nickel