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제117회 대한화학회 학술발표회, 총회 및 기기전시회 Crystallographic and spectroscopic characterization and reactivities of a mononuclear non-haem iron(III)-superoxo complex

2016년 3월 23일 16시 05분 44초
KCS2.O-6 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
목 11시 : 10분
한국다우케미칼 우수논문상 수상자 구두발표
저자 및
홍승우, Kyle D. Sutherlin, 박지영, 권은지, Maxime A. Siegler, Edward I. Solomon, 남원우*
이화여자대학교 화학나노과학과, Korea

Mononuclear nonheme iron(III)-superoxo species (FeIII-O2–•) have been implicated as key intermediates in the catalytic cycles of dioxygen activation by nonheme iron enzymes. Although nonheme iron(III)-superoxo species have been trapped and characterized spectroscopically in enzymatic and biomimetic reactions, no structural information has yet been obtained. Here we report for the first time the isolation, spectroscopic characterization, and crystal structure of a mononuclear side-on (η2) iron(III)-superoxo complex with a tetraamido macrocyclic ligand (TAML), [FeIII(TAML)(O2)]2– (1). The nonheme iron(III)-superoxo species undergoes both electrophilic and nucleophilic oxidation reactions as well as O2-transfer between metal complexes. In the O2-transfer reaction, 1 transfers the bound O2 unit to a manganese(III) analogue, resulting in the formation of a manganese(IV)-peroxo complex, [MnIV(TAML)(O2)]2– (2); 2 is characterized structurally and spectroscopically as a mononuclear side-on (η2) manganese(IV)-peroxo complex. The difference in the redox distribution between the metal ions and O2 in 1 and 2 is rationalized using density functional theory calculations.