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The Heterolytic O-O Bond Cleavage of Putative Nonheme Iron(II)-OOH(R) Complexes, and Characterization and Reactivity of Nonheme Iron(V)-Imido Complex

Title
The Heterolytic O-O Bond Cleavage of Putative Nonheme Iron(II)-OOH(R) Complexes, and Characterization and Reactivity of Nonheme Iron(V)-Imido Complex
Authors
박소라
Issue Date
2016
Department/Major
대학원 화학·나노과학과
Publisher
이화여자대학교 대학원
Degree
Master
Advisors
남원우
Abstract
We have studied comparison of one-electron reduction of mononuclear nonheme complexes by Fc derivatives. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, indicating that the complexes to their one-electron reduced species is the rate determining step, followed by the heterolytic O-O bond cleavage of the putative iron(II)-(hydro/alkyl)peroxo species to give the iron(IV)-oxo complexes. We report the differences in the reactivity of the heterolytic and homolysis O-O bond cleavage on the basis of the detailed comparison of these species. In the second part, we have successfully synthesized and characterized high-valent iron(V)-imido complex bearing tetraanionic ligand, [FeV(NTs)(TAML)]-. We also examined the reactivity studies in C-H amination reaction via H-atom abstraction and nitrene transfer reaction to sulphur containing substrates.;본 연구에서는 Fc derivatives에 의한 단핵 비헴성 Iron(III)-(hydro/alkyl)peroxo 화합물의 일-전자 환원에 대한 연구를 수행하였다. 전자주개의 농도와 산화전위에 의해 전환-속도가 결정되며Iron(III)-(hydro/alkyl)peroxo 화합물이 전자주개에 의해 Iron(II)-(hydro/alkyl)peroxo 종이 되며, Iron(II)-(hydro/alkyl)peroxo 종이 O-O 결합 불균등 해리에 의해 iron(IV)-oxo화합물이 생성되는 메커니즘을 규명하였다. 이 때 속도 결정 단계가 전자-전달 과정임을 확인할 수 있었다. 2 장에서는, tetraanionic tetraamidomacrocyclic ligand (TAML)가 배위된 고-산화가 iron(V)-imido 화합물을 성공적으로 합성하고 특성을 밝혔다. 또한 H-atom abstraction을 통한C-H 아미노화반응과 Sulphur 를 포함한 기질들의 nitrene 전이 반응을 통해 반응성을 관찰하였다.
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일반대학원 > 화학·나노과학과 > Theses_Master
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