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dc.description.abstractWe 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.-
dc.description.tableofcontentsPart I 1 Abstract 2 I. Introduction 3 II. Materials and Methods 6 II-1. Materials 6 II-2. Instrumentations 6 II-3. Generation of [(14-TMC)FeIII-OOH]2+ 6 II-4. Generation of [(13-TMC)FeIII-OOC(CH3)3] 2+ and [(13-TMC)FeIII-OOCm] 2+ 7 II-5. Kinetic Measurements 7 II-6. Product Analysis 8 II-7. DFT calculations 8 III. Results and Discussion 10 III-1. Generation of [(14-TMC)FeIII-OOH]2+ 10 III-2. Generation of [(13-TMC)FeIII-OOC(CH3)3] 2+ and [(13-TMC)FeIII-OOCm] 2+ 10 III-3. Reactivity of [(14-TMC)FeIII-OOH]2+ 12 III-4. Reactivity of [(13-TMC)FeIII-OOC(CH3)3] 2+ 18 III-5. Comparison of Reactivity Studies on [(14-TMC)FeIII-OOH]2+ and [(13-TMC)FeIII-OOC(CH3)3] 2+ 22 III-6. Charaterizaion of [(14-TMC)FeIII-OOH]2+ and [(13-TMC)FeIII-OOC(CH3)3] 2+ 26 IV. Conclusion 30 References 31 Part II 34 Abstract 35 I. Introduction 36 II. Materials and Methods 38 II-1. Materials 38 II-2. Generation of [Fe(NTs)TAML]- 38 II-3. UV-Vis Spectroscopy 38 II-4. CSI-TOF MS Measurements 38 II-5. EPR Measurements 39 II-6. rRaman Measurements 39 III. Results and Discussion 40 III-1. Generation and characterization of [FeV(NTs)TAML] 40 III-2. Reactivity of [FeV(NTs)TAML] (1) in C-H bond activation reactions 45 III-3. Reactivity of [FeV(NTs)TAML] (1)in nitrene transfer reactions 50 IV. Conclusion 54 References 55 국문초록 58-
dc.format.extent1917343 bytes-
dc.publisher이화여자대학교 대학원-
dc.titleThe Heterolytic O-O Bond Cleavage of Putative Nonheme Iron(II)-OOH(R) Complexes, and Characterization and Reactivity of Nonheme Iron(V)-Imido Complex-
dc.typeMaster's Thesis-
dc.creator.othernamePark, Sora-
dc.format.pagexi, 68 p.-
dc.identifier.major대학원 화학·나노과학과- 2-
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