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Tuning the Reactivity of Chromium(III)-Superoxo Species by Coordinating Axial Ligands

Tuning the Reactivity of Chromium(III)-Superoxo Species by Coordinating Axial Ligands
Goo, YR[Goo, Yi Re]Maity, AC[Maity, Annada C.]Cho, KB[Cho, Kyung-Bin]Lee, YM[Lee, Yong-Min]Seo, MS[Seo, Mi Sook]Park, YJ[Park, Young Jun]Cho, J[Cho, Jaeheung]Nam, W[Nam, Wonwoo]
DGIST Authors
Cho, J[Cho, Jaeheung]
Issue Date
Inorganic Chemistry, 54(21), 10513-10520
Article Type
ChemistryChromiumKineticsLigandLigandsOxidation-ReductionOxidation-Reduction ReactionSpectrophotometry, UltravioletUltraviolet Spectrophotometry
Metal-superoxo species have attracted much attention recently as key intermediates in enzymatic and biomimetic oxidation reactions. The effect(s) of axial ligands on the chemical properties of metal-superoxo complexes has never been explored previously. In this study, we synthesized and characterized chromium(III)-superoxo complexes bearing TMC derivatives with pendant pyridine and imidazole donors, such as [CrIII(O2)(TMC-Py)]2+ (1, TMC-Py = 4,8,11-trimethyl-1-(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane) and [CrIII(O2)(TMC-Im)]2+ (2, TMC-Im = 4,8,11-trimethyl-1-(2-methylimidazolmethyl)-1,4,8,11-tetraazacyclotetradecane). The reactivity of chromium(III)-superoxo complexes binding different axial ligands, such as 1, 2, and [CrIII(O2)(TMC)(Cl)]+ (3, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was then investigated in C-H bond activation and oxygen atom transfer reactions. Kinetic studies revealed that the reactivity of the Cr(III)-superoxo complexes depends on the axial ligands, showing the reactivity order of 1 > 2 > 3 in those electrophilic oxidation reactions. It was also shown that there is a good correlation between the reactivity of the chromium(III)-superoxo complexes and their redox potentials, in which the redox potentials of the chromium(III)-superoxo complexes are in the order 1 > 2 > 3. DFT calculations reproduced the reactivity order between 1 and 3 in both C-H bond activation and oxygen atom transfer reactions, and the latter reaction is described using orbital interactions. The calculations are also in agreement with the experimentally obtained redox potentials. The present results provide the first example showing that the reactivity of metal-superoxo species can be tuned by the electron-donating ability of axial ligands bound trans to the metal-superoxo moiety. © 2015 American Chemical Society.
American Chemical Society
Related Researcher
  • Author Cho, Jaeheung Biomimetic Materials Laboratory
  • Research Interests Biomimetics; Metalloenzymes; Nitric Oxide Suppliers in Brain; Biomimetic Materials in Life
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Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles

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