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.
Original language | English |
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Pages (from-to) | 1502-1508 |
Number of pages | 7 |
Journal | Chemical Science |
Volume | 4 |
Issue number | 4 |
DOIs | |
State | Published - 4 Mar 2013 |