Full metadata record
DC Field | Value | Language |
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dc.contributor.advisor | 남원우 | - |
dc.contributor.author | 윤희정 | - |
dc.creator | 윤희정 | - |
dc.date.accessioned | 2016-08-26T04:08:19Z | - |
dc.date.available | 2016-08-26T04:08:19Z | - |
dc.date.issued | 2013 | - |
dc.identifier.other | OAK-000000077093 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/209904 | - |
dc.identifier.uri | http://dcollection.ewha.ac.kr/jsp/common/DcLoOrgPer.jsp?sItemId=000000077093 | - |
dc.description.abstract | Investigation of electron-transfer properties of a nonheme Mn(IV)-oxo complex, [(Bn-TPEN)MnIV(O)]2+ (Bn-TPEN = N-benzyl-N,N’,N’-tris(2-pyridylmethyl)-1,2-diaminoethane), reveals that Mn(IV)-oxo complex acts as a stronger one-electron oxidant than the Fe(IV)-oxo analogue. We have determined for the first time the fundamental electron-transfer properties of a nonheme MnIV(O) complex, which is featured by a highly positive one-electron reduction potential, as compared with those of nonheme FeIV(O) complexes. As a result of the highly positive one-electron reduction potential, the occurrence of electron transfer in the N-dealkylation of DMA derivatives has been confirmed by the detection of radical cation intermediate, para-methyl-DMA•+, in the oxidation of para-methyl-DMA by the nonheme MnIV(O) complex, [(Bn-TPEN)MnIV(O)]2+.;본 연구에서는 nonheme manganese(IV)-oxo 종인 [(Bn-TPEN)-MnIV(O)]2+ (Bn-TPEN = N-benzyl-N,N’,N’-tris(2-pyridylmethyl)-1,2-diaminoethane)의 가장 기본적인 전자전달 반응의 특성과 의미에 중점을 두었다. 여러 전자 주개들을 통하여 [(Bn-TPEN)MnIV(O)]2+ 의 전자전달 반응을 통하여 열역학적, 반응속도론적 성질을 알아내었다. 그 결과, [(Bn-TPEN)MnIV(O)]2+은 nonheme iron(IV)-oxo 종 보다 더 강력한 일전자 산화제로서 작용할 수 있다는 것을 밝혀내었으며 이는 기존에 알려진 금속-옥소 종 가운데 가장 높은 일전자 환원력을 가진다는 것에 큰 의의를 가지고 있따. 따라서 금속-옥소 종과 DMA 유도체들의 반응인N-dealkylation에서의 일전자 전달을 para-methyl-DMA•+을 분광학적으로 확인할 수 있었으며, 뿐 아니라, 전자 전달에 관한 Marcus theory에 의하여 전자 전달 속도의 driving force dependence를 분석하므로써 reorganization energy (λ)를 얻을 수 있었다. | - |
dc.description.tableofcontents | I. Introduction 1 II. Materials and Method 3 II-1.Materials 3 II-2.Spectral Redox Titration 3 II-3.Instruments 4 III.Results and Discusstion 6 III-1.Generation of [(Bn-TPEN)MnIV(O)]2+ 6 III-2.Equilibrium Constant, Ket, of Electron-Transfer of [(Bn-TPEN)MnIV(O)]2+ by Dibromoferrocene 13 III-3.One-Electron Reduction Potential, Ered, of [(Bn-TPEN)MnIV(O)]2+ 17 III-4.Driving Force of [(Bn-TPEN)MnIV(O)]2+ Electron Transfer 18 III-5.N-dealkylation of para-methyl-DMA by [(Bn-TPEN)MnIV(O)]2+ with the Detection of para-methyl-DMA Radical Cation 26 IV.Conclusion 30 V.References 31 국문초록 36 | - |
dc.format | application/pdf | - |
dc.format.extent | 1579993 bytes | - |
dc.language | eng | - |
dc.publisher | 이화여자대학교 대학원 | - |
dc.subject.ddc | 600 | - |
dc.title | Electron-transfer properties of a nonoheme manganese(IV)-oxo complex acting as a stronger one-electron oxidant than the iron(IV)-oxo analogue | - |
dc.type | Master's Thesis | - |
dc.format.page | ix, 37 p. | - |
dc.identifier.thesisdegree | Master | - |
dc.identifier.major | 대학원 바이오융합과학과 | - |
dc.date.awarded | 2013. 2 | - |