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Mononuclear nickel(II)-superoxo and nickel(III)-peroxo complexes bearing a common macrocyclic TMC ligand

Mononuclear nickel(II)-superoxo and nickel(III)-peroxo complexes bearing a common macrocyclic TMC ligand
Cho, J[Cho, Jaeheung]Kang, HY[Kang, Hye Yeon]Liu, LV[Liu, Lei V.]Sarangi, R[Sarangi, Ritimukta]Solomon, EI[Solomon, Edward I.]Nam, W[Nam, Wonwoo]
DGIST Authors
Cho, J[Cho, Jaeheung]
Issued Date
Article Type
Catalytic CyclesDensity Functional TheoryDFT CalculationDioxygen ActivationElectronic StructureElectrophilic CharacterLigandsMacrocyclicsMetalloenzymesNickelNickel CompoundsNucleophilic ReactionOrganic SubstratePeroxo LigandsPeroxocomplexesPorphyrinsReactivity StudiesRing SizesSpectroscopic AnalysisSynthesis (Chemical)Tetramethyl Ammonium HydroxideTheoretical StudyTriethylaminesVarious Spectroscopic MethodsX Ray Crystallography
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-O2 core 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 H 2O2 in 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)(O 2)]+ is bound in an end-on fashion to the nickel(ii) center, whereas the peroxo ligand in [NiIII(13-TMC)(O 2)]+ 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. © The Royal Society of Chemistry 2013.
Royal Society of Chemistry
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Department of Physics and Chemistry Biomimetic Materials Laboratory 1. Journal Articles


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