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114th General Meeting of Korean Chemical Society Synthesis, Characterization, and Reactivities of Mononuclear Cobalt(III)-Hydroperoxo Complex

Submission Date :
8 / 28 / 2014 , 15 : 21 : 01
Abstract Number :
114082810798
Presenting Type:
Poster Presentation
Presenting Area :
무기화학
Authors :
신봉기, 조재흥*
대구경북과학기술원(DGIST) 신물질과학, Korea
Assigned Code :
INOR.P-233 Assigend Code Guideline
Presenting Time :
10월 15일 (수요일) 16:00~19:00
Metal-dioxygen adducts, such as metal-peroxo and -hydroperoxo species, are key intermediates that observed in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. Previously, manganese(III)-hydroperoxo complex, [Mn(III)(TMC)(OOH)]2+ (TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) was characterized and reactivity of this intermediate has been shown electrophilic character. In this work, using Me3-TPADP (Me3-TPADP=3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane) ligand, [Co(II)(Me3-TPADP)(CH3CN)2]2+ was synthesized and characterized. Cobalt(III)-peroxo complex, [Co(III)(Me3-TPADP)(O2)]+, was synthesized with H2O2 in the presence of triethylamine. Upon protonation, Co(III)-peroxo complex was converted into a Co(III)-hydroperoxo complex, [Co(III)(Me3-TPADP)(OOH)(CH3CN)]2+. Interestingly, the Co(III)-hydroperoxo complex shows both nucleophilic and electrophilic reactivity.