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dc.contributor.advisor 조재흥 - Oh, Seongmin - 2020-08-06T06:15:47Z - 2020-08-06T06:15:47Z - 2020 -
dc.identifier.uri en_US
dc.identifier.uri -
dc.description Co(III)-hydroperoxo complexes, Electronic effect, Oxygen atom transfer -
dc.description.abstract Metal-O2 adducts such as metal-hydroperoxo species play critical roles in metabolism mediated by Metalloenzymes. These metalloenzymes are known to have varying selectivity and reactivity depending on the electronic effect obtained from substituents in the second coordination sphere. Herein, Cl2-TBDAP and OMe2-TBDAP were synthesized as derivatives of a macrocyclic N4-type tetradentate TBDAP ligand (TBDAP = N,N′-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane). Three cobalt(III)-hydroperoxo complexes, [CoIII(Cl2-TBDAP)(O2H)(CH3CN)]2+, [CoIII(TBDAP)(O2H)(CH3CN)]2+ and [CoIII((OMe)2-TBDAP)(O2H)(CH3CN)]2+, were synthesized and characterized with various physicochemical methods, such as UV-vis, ESI-MS and resonance Raman. The electrochemical studies reveal that difference of electronic properties was derived by the substituents at the para-position of the pyridine rings of TBDAP. In the phosphine oxidation of PPh3, the reaction rates of the cobalt(III)-hydroperoxo complexes were observed to be in the order of [CoIII((OMe)2-TBDAP)(O2H)(CH3CN)]2+ > [CoIII(TBDAP)(O2H)(CH3CN)]2+ > [CoIII(Cl2-TBDAP)(O2H)(CH3CN)]2+. This difference in the reactivity may have been derived from the electronic effect of the substituents in the para-position of the pyridine rings in supporting ligands. -
dc.description.statementofresponsibility N -
dc.description.tableofcontents Abstract i
List of contents ii
List of tables iii
List of figures iv

Ⅰ. Introduction

1.1 Introduction 1

II. Experimental Session

2.1 Materials and Instrumentation 4
2.2 Synthesis 5
2.2.1 4-chloro-2,6-bis(chloromethyl)pyridine 5
2.2.2 4-chloropyridine-2,6-dicarbardehyde 5
2.2.3 N,N’-(4-chloropyridine-2,6-diyl)bis(methylene)bis(2-methylpropan-2-amine) 5
2.2.4 N,N’-di-tert-butyl-2,11-diaza[3,3](2,6)-4-chloropyridinophane (Cl2-TBDAP) 5
2.2.5 N,N’-di- tert-butyl-2,11-diaza[3,3](2,6)-4-methoxypyridinophane ((OMe)2-TBDAP) 6
2.2.6 [CoII(Cl2-TBDAP)(NO3)2] 6
2.2.7 [CoII((OMe)2-TBDAP)(NO3)]+ 6
2.3 X-ray crystallography 7
2.4 Reactivity 10

III. Results and Discussion

3.1 Synthesis and Characterization of Co(II) starting complexes 11
3.2 Synthesis and Characterization of Co(III)-peroxo complexes 18
3.3 Synthesis and Characterization of Co(III)-hydroperoxo complexes 23
3.4 Reactivity of Co(III)-hydroperoxo complexes 25

IV. Conclusion
dc.format.extent 43 -
dc.language eng -
dc.publisher DGIST -
dc.title Controlling the Reactivity of Co(III)-Hydroperoxo Species by Tuning Electronic Property of TBDAP Ligand -
dc.type Thesis -
dc.identifier.doi 10.22677/thesis.200000321099 -
dc.description.alternativeAbstract 본 논문은 코발트 하이드로퍼옥소 종에서 일어나는 산화 반응에 관한 것이다. 생체 내에 있는 금속 효소들은 산소와 같은 분자들을 활성화시켜 자연에 존재하고 있는 물질을 전환시키거나 산화적 대사, 인산화와 같은 다양한 반응들을 매개한다. 따라서 효소들의 생체 내 작용 기작에 대한 연구를 하기 위해 새로운 코발트 모델 화합물을 합성하였고, 산소 활성화를 통해 반응 중간체인 코발트 하이드로퍼옥소 종을 합성하였다.
본 논문에서는 피리딘 고리의 파라 위치 작용기가 클로로기와 메톡시기로 치환된 TBDAP 배위자 유도체를 이용한 코발트 중간체를 합성하였고 순환전류법을 통한 분석 결과 TBDAP 배위자에 있는 피리딘 고리의 치환기에 따라 서로 다른 전자적 효과가 유도되었음이 확인되었다. 또한 코발트 하이드로퍼옥소종과 외부 기질과의 반응성을 관찰한 결과 배위자 피리딘 고리의 치환기에 따라 약 45 배의 반응 속도 차이가 있음을 확인하였다. 이러한 반응성 차이는 앞서 언급한 전자적 효과의 차이에 의한 것으로 예측된다.
본 논문의 TBDAP 배위자 유도체 및 이를 이용해 합성한 코발트 하이드로퍼옥소 화합물은 생체 내에서 일어나는 다양한 산화 반응의 반응 기작을 규명하는 데에 도움을 줄 수 있다.
- Master -
dc.contributor.department Department of Emerging Materials Science -
dc.contributor.coadvisor Lee, Sunggi - 2020/08 -
dc.publisher.location Daegu -
dc.description.database dCollection -
dc.citation XT.MM오54C 202008 - 7/23/20 -
dc.contributor.alternativeDepartment 신물질과학전공 -
dc.embargo.liftdate 8/31/25 -
dc.contributor.affiliatedAuthor Oh, Seongmin -
dc.contributor.affiliatedAuthor Cho, Jaeheung -
dc.contributor.affiliatedAuthor Lee, Sunggi -
dc.contributor.alternativeName 오성민 -
dc.contributor.alternativeName Cho, Jaeheung -
dc.contributor.alternativeName 이성기 -
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