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제109회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Olefin Epoxidation of Nonheme Cobalt(III) Catalyst: Partition of Multiple Active Oxidants CoV=O, CoIV=O, and CoIII-OO(O)CR Species

등록일
2012년 2월 7일 11시 28분 52초
접수번호
0080
발표코드
INOR.P-122 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
4월 25일 (수요일) 18:00~21:00
발표형식
포스터
발표분야
무기화학
저자 및
공동저자
현민영, 배정미, 김현, 김경범, 김철
서울과학기술대학교 정밀화학과, Korea
A mononuclear nonheme cobalt(III) complex of a tetradentate ligand containing two deprotonated amide moieties, [Co(bpc)Cl2][Et4N] (1), were prepared and then characterized by IR, elemental analysis, UV-vis and electron paramagnetic resonance spectroscopy. Complex 1 was also characterized by X-ray crystallography. This nonheme CoIII complex catalyzes olefin epoxidation upon treatment with meta-chloroperbenzoic acid. It is proposed that complex 1 shows partitioning between the heterolytic and homolytic cleavage of an O-O bond to afford CoV=O and CoIV=O intermediates, proposed to be responsible for the stereospecific olefin epoxidation and radical-type oxidations, respectively. Moreover, under extreme conditions, where the concentration of an active substrate is very high, the Co-OOC(O)R (2) might be a possible reactive species for epoxidation. Evidence for these multiple active oxidants was derived from product analysis, the use of peroxyphenylacetic acid as peracid and EPR measurements. Our results suggest that a less accessible CoV=O moiety can form in a system wherein the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors.

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