Dioxygen Activation by Biomimetic Mononuclear Iron(II) Complexes and Ligand Topology Effect on the Reactivity of Mononuclear Nonheme Iron(IV)-Oxo Complex in Oxygenation Reactions
- 주제(키워드) dioxygen activation , ligand topology
- 발행기관 서강대학교 일반대학원
- 지도교수 신운섭
- 발행년도 2012
- 학위수여년월 2012. 2
- 학위명 박사
- 학과 및 전공 일반대학원 바이오융합기술협동과정
- 실제URI http://www.dcollection.net/handler/sogang/000000047399
- 본문언어 영어
- 저작권 서강대학교 논문은 저작원 보호를 받습니다.
초록/요약
We now report that a non-heme iron(II) complex activates O2 and generates its corresponding iron(III)-hydroperoxo or high-valent iron(IV)-oxo intermediates in presence of NADH analogue and proton source or substrates with weak C-H bonds (e.g., olefins and alkylaromatic compounds). We propose that a putative iron(III)-superoxo intermediate initiates the O2-activation chemistry by protonation itself or abstracting a H atom from the substrate, with subsequent generation of a high-valent iron(IV)-oxo intermediate from the resulting iron(III)-hydroperoxo species. On the other hand, we also emphasize the effective influence of ligand topology in reactivity of iron(IV)-oxo intermediate by synthesizing two iron model compounds which contain same ligand with different configuration.
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