title: Mononuclear nickel(II)-superoxo and nickel(III)-peroxo complexes bearing a common macrocyclic TMC ligand.
abstract: Mononuclear metal-dioxygen adducts, such as metal-superoxo and -peroxo species, are generated as key intermediates in the catalytic cycles of dioxygen activation by heme and non-heme metalloenzymes. We have shown recently that the geometric and electronic structure of the Ni-O2core in [Ni(n-TMC)(O2)]+(n= 12 and 14) varies depending on the ring size of the supporting TMC ligand. In this study, mononuclear Ni(II)-superoxo and Ni(III)-peroxo complexes bearing a common macrocylic 13-TMC ligand, such as [NiII(13-TMC)(O2)]+and [NiIII(13-TMC)(O2)]+, were synthesized in the reaction of [NiII(13-TMC)(CH3CN)]2+and H2O2in the presence of tetramethylammonium hydroxide (TMAH) and triethylamine (TEA), respectively. The Ni(II)-superoxo and Ni(III)-peroxo complexes bearing the common 13-TMC ligand were successfully characterized by various spectroscopic methods, X-ray crystallography, and DFT calculations. Based on the combined experimental and theoretical studies, we conclude that the superoxo ligand in [NiII(13-TMC)(O2)]+is bound in an end-on fashion to the nickel(II) center, whereas the peroxo ligand in [NiIII(13-TMC)(O2)]+is bound in a side-on fashion to the nickel(III) center. Reactivity studies performed with the Ni(II)-superoxo and Ni(III)-peroxo complexes toward organic substrates reveal that the former possesses an electrophilic character, whereas the latter is an active oxidant in nucleophilic reaction.
authors: Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea. ; Department of Emerging Materials Science, DGIST, Daegu 711-873, Korea.
authors: Jaeheung
authors: J
authors: Cho
authors: Hye Yeon
authors: HY
authors: Kang
authors: Lei V
authors: LV
authors: Liu
authors: Ritimukta
authors: R
authors: Sarangi
authors: Edward I
authors: EI
authors: Solomon
authors: Wonwoo
authors: W
authors: Nam
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