title: Dioxygen activation and substrate oxygenation by a p-nitrothiophenolatonickel complex: unique effects of an acetonitrile solvent and the p-nitro group of the ligand.
abstract: The nickel(II) complex [Ni(Tp(Me2)) (SC(6)H(4)NO(2))] [1a; Tp(Me2) = hydrotris(3,5-dimethylpyrazol-1-yl)borate] reacts with O(2) to form the ligand oxygenation product ArSO(2)(-) in MeCN, and also 1a catalyzes the oxygenation of external substrates such as triphenylphosphine. The reactivity may correlate to the unique quinoid-like resonance structure of the thiophenolate ligand. The structure is stabilized by a p-nitro group and induced by coordination of MeCN.
authors.affiliation: Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686 Japan.
authors.forename: Jun
authors.initials: J
authors.lastname: Nakazawa
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Ogiwara
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Kashiwazaki
authors.forename: Akiyoshi
authors.initials: A
authors.lastname: Ishii
authors.forename: Naoki
authors.initials: N
authors.lastname: Imamura
authors.forename: Yuya
authors.initials: Y
authors.lastname: Samejima
authors.forename: Shiro
authors.initials: S
authors.lastname: Hikichi
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D009532:Nickel / Q000737:chemistry*; D009574:Nitro Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D056831:Coordination Complexes; D008024:Ligands; D009574:Nitro Compounds; D012997:Solvents; D009532:Nickel; D010100:Oxygen; C032159:acetonitrile