Dioxygen activation and substrate oxygenation by a p-nitrothiophenolatonickel complex: unique effects of an acetonitrile solvent and the p-nitro group of the ligand |
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Authors: | Nakazawa Jun Ogiwara Hiroyuki Kashiwazaki Yusuke Ishii Akiyoshi Imamura Naoki Samejima Yuya Hikichi Shiro |
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Institution: | Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686 Japan. |
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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. |
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