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학술발표회초록보기

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제109회 대한화학회 학술발표회, 총회 및 기기전시회 안내 A Mononuclear 'side-on' Chromium(IV)-Peroxo Complex : Crystallographic and Spectroscopic Characterization and Reactivity

등록일
2012년 2월 29일 14시 38분 33초
접수번호
1528
발표코드
INOR.P-262 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
4월 25일 (수요일) 18:00~21:00
발표형식
포스터
발표분야
무기화학
저자 및
공동저자
한정은, 조재흥1, 남원우2
이화여자대학교 바이오융합과, Korea
1이화여자대학교 나노과학부, Korea
2이화여자대학교 화학과, Korea

Metal dioxygen adducts, such as metal-superoxo and -peroxo species, are key intermediates detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. The synthesis and spectroscopic characterization of an end-on Cr(III)-superoxo complex with a 14-membered macrocyclic ligand and its reactivity in C-H bond activation (e.g., electrophilic reactivity) was reported previously. In this work, Cr(IV)-peroxo complex, [CrIV(12-TMC)(O2)(Cl)]+ (12-TMC=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane), was synthesized by changing ring size of the mycrocyclic ligand, and characterized with X-ray crystallography and spectroscopic methods such as UV-vis absorption, electrospray ionization mass, EPR, resonance Raman. In contrast to the end-on Cr(III)-superoxo complex, the Cr(IV)-peroxo complex was not reactive in electrophilic reactions but was capable of deformylating aldehydes via nucleophilic reaction. These results indicate the significance of supporting ligands in tuning the geometric and electronic structures and reactivity of metal-O2 intermediates that have been shown to have biological as well as synthetic usefulness in biomimetic reactions.


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