title: Characterization of one-electron oxidized copper(II)-salophen-type complexes; effects of electronic and geometrical structures on reactivities.
abstract: One-electron oxidized salophen-type complexes, [Cu(salophen)](+) (H2salophen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminobenzene), and its methoxy derivatives, [Cu(MeO-salophen)](+) and [Cu(salophen-(MeO)2)](+) (H2MeO-salophen = N,N'-bis(3-tert-butyl-5-methoxysalicylidene)-1,2-diaminobenzene, H2salophen-(MeO)2 = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diamino-4,5-dimethoxybenzene), have been synthesized and structurally characterized, and their reactivities have been investigated. The solid state structures of the one-electron oxidized forms of these complexes suggested that [Cu(salophen)](+) and [Cu(MeO-salophen)](+) can be assigned to relatively localized Cu(ii)-phenoxyl radical complexes, while [Cu(salophen-(MeO)2)](+) is the diiminobenzene radical complex. On the other hand, [Cu(salophen)](+) in solution showed a different electronic structure from that of the solid sample, the radical electron being delocalized over the whole π-conjugated ligand. The reaction of these oxidized complexes with benzyl alcohol has been investigated in the presence of a large excess of substrate, which revealed the difference in the kinetic behavior between the complexes. The mechanisms of the oxidation have been discussed on the basis of the electronic and geometrical structures and the reaction kinetics.
authors.affiliation: College of Science, Ibaraki University, Bunkyo, Mito 310-8512, Japan. yshima@mx.ibaraki.ac.jp.
authors.forename: Kazutaka
authors.initials: K
authors.lastname: Asami
authors.forename: Akiko
authors.initials: A
authors.lastname: Takashina
authors.forename: Misato
authors.initials: M
authors.lastname: Kobayashi
authors.forename: Satoshi
authors.initials: S
authors.lastname: Iwatsuki
authors.forename: Tatsuo
authors.initials: T
authors.lastname: Yajima
authors.forename: Amélie
authors.initials: A
authors.lastname: Kochem
authors.forename: Maurice
authors.initials: M
authors.lastname: van Gastel
authors.forename: Fumito
authors.initials: F
authors.lastname: Tani
authors.forename: Takamitsu
authors.initials: T
authors.lastname: Kohzuma
authors.forename: Fabrice
authors.initials: F
authors.lastname: Thomas
authors.forename: Yuichi
authors.initials: Y
authors.lastname: Shimazaki
mesh_terms: D019905:Benzyl Alcohol / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004583:Electrons; D008958:Models, Molecular; D012459:Salicylates / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D012459:Salicylates; C090416:salophen; D003300:Copper; D019905:Benzyl Alcohol