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dc.contributor.advisor Cho, Jae Heung -
dc.contributor.author Kim, Ja lee -
dc.date.accessioned 2017-05-10T08:51:00Z -
dc.date.available 2017-02-13T00:00:00Z -
dc.date.issued 2015 -
dc.identifier.uri http://dgist.dcollection.net/jsp/common/DcLoOrgPer.jsp?sItemId=000001923133 en_US
dc.identifier.uri http://hdl.handle.net/20.500.11750/1378 -
dc.description.abstract The reactivity of mononuclear metal-O2 adducts, such as metal-superoxo and -peroxo species, has long fascinated researchers in many areas due to the significance of diverse biological and catalytic processes. To understand how the nature of the ligand influences reactivity patterns of the metal-O2 complexes, recently, a systematic study of the relationship between reactivity and ring size of ligand was undertaken for a series of metal-O2 complexes bearing N-tetramethylated macrocyclic chelates in biomimetic chemistry. In this study, the two ligands, CHDAP and Me3-TPADP, were designed and reactivity of Ni-O2 species bearing each ligand was investigated in part I and part II, respectively. For comparison of reactivity according to a steric effect, a set of nickel(III)-peroxo complexes bearing tetraazamacrocyclic ligands, [NiIII(CHDAP)(O2)]+ and [NiIII(TBDAP)(O2)]+, were prepared and fully characterized by various physicochemical methods. The different steric properties of the supporting ligands were confirmed by X-ray crystallography where the CHDPA ligand gives enough space around the Ni-O2 core compared to the TBDAP ligand. In the aldehyde deformylation reaction, the nucleophilic reactivity of the nicke(III)-peroxo complexes was highly dependent on the steric properties of the macrocyclic ligands, with the reactivity order of [NiIII(TBDAP)(O2)]+ < [NiIII(CHDAP)(O2)]+. This result provides fundamental insight into the mechanism of the structure (steric) – reactivity relationship of metal-peroxo intermediates. In part II, the Me3-TPADP ligand was synthesized, and the starting complex, [NiII(Me3-TPADP)(CH3CN)2]2+ (3), and Ni-O2 intermediate, [NiIII(Me3-TPADP)(O2)]+ (4), were prepared and successfully characterized by various methods. Also, the kinetic result of 4 was obtained with external organic substrates. ⓒ 2015 DGIST -
dc.description.tableofcontents Part I. A Steric Effect on the Nucleophilic Reactivity of Nickel(III)-O2 Complex 1--
I. Introduction 2--
II. Experimental Section 7--
II-1. Materials and Instrumentation 7--
II-2. Synthesis of Pyridinophan Type Ligands 8--
II-2-a. Pyridine-2,6-dicarbaldehyde (L1) 8--
II-2-b. N,N’-(pyridine-2,6-diylbis(methylene))dicyclohexylamine (L2) 9--
II-2-c. 2,6-bis(chloromethyl)pyridine (L3) 9--
II-2-d. N,N’-di-cyclohexyl-2,11-diaza[3,3](2,6)pyridinophane (CHDAP) 9--
II-3. Generation of Ni Complexes 10--
II-3-a. [Ni(CHDAP)(NO3)]+ (1) 10--
II-3-b. [Ni(CHDAP)(O2)]+ (2) 10--
II-4. X-ray Crystallography 11--
II-5. Reactivity Studies 11--
III. Results and Discussion 13--
III-1. Synthesis and Characterization of CHDAP 13--
III-2. Preparation and Characterization of [NiII(CHDAP)(NO3)]+ (1) 15--
III-3. Characterization and Reactivity Studies of [NiIII(CHDAP)(O2)]+ (2) 19--
III-4. Comparison with Ni Complex bearing TBDAP Ligand 26--
IV. Conclusion 29--
V. References 30--
Part II. Synthesis, Characterization and Reactivity of a Mononuclear Nickel(III)-O2 Complex with Macrocyclic Ligand, Me3-TPADP 36--
I. Introduction 37--
II. Experimental Section 40--
II-1. Materials and Instrumentation 40--
II-2. Synthesis of Ligands 41--
II-2-a. 1,4,7-tris(p-tosylsulfonyl)-1,4,7-triazaheptane (L4) 41--
II-2-b. 3,6,9-tris(p-tosylsulfonyl)-3,6,9,15-tetraazbicyclo[9,3,1]pentadeca-1(15),11,13-triene (L5) 42--
II-2-c. 3,6,9,15-tetraazabocyclo(9,3,1)pentadeca-1(15),11,13-triane (L6) 42--
II-2-d. 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane (Me3-TPADP) 42--
II-3. Generation of Ni Complexes 43--
II-3-a. [Ni(Me3-TPADP)(CH3CN)2] 2+ (3) 43--
II-3-b. [Ni(Me3-TPADP)(O2)]+ (4) 43--
II-4. X-ray Crystallography 44--
II-5. Reactivity Studies 44--
III. Results and Discussion 45--
III-1. Synthesis and Characterization of Me3-TPADP 45--
III-2. Preparation and Characterization of [NiII(Me3-TPADP)(CH3CN)2]2+ (3) 47--
III-3. Characterization and Reactivity Studies of [NiIII(Me3-TPADP)(O2)]+ (4) 51--
IV. Conclusion 56--
V. References 57
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dc.format.extent 60 -
dc.language eng -
dc.publisher DGIST -
dc.subject Ni-O2 -
dc.subject steric effect -
dc.subject electronic effect -
dc.subject kinetic -
dc.title Synthesis, Characterization and Reactivity Control of Ni-Oxygen Adducts with Organic Substrates -
dc.type Thesis -
dc.identifier.doi 10.22677/thesis.1923133 -
dc.description.alternativeAbstract 생체 내 촉매 반응에 있어서 단일 금속-산소 종은 산화 환원 과정의 중요한 중간체 역할을 하기에 많이 연구되어 왔다. 리간드가 금속-산소 복합체의 반응성 패턴에 미치는 영향을 이해하기 위해, 최근, N-tetramethylated 거대 고리 킬레이트가 부착된 몇몇 금속-산소 복합체에서 N-리간드의 고리 크기와 반응성 사이의 관계에 대한 체계적인 공부가 진행되었다. 이번 연구에서, CHDAP 그리고 Me3-TPADP 리간드가 디자인되었고 각각의 리간드가 부착된 니켈-산소 종의 반응성은 part I 그리고 part II에서 각각 조사되었다. 구조적 영향에 따른 반응성의 비교를 위해 형성된 니켈(III)-peroxo 복합체, [NiIII(CHDAP)(O2)]+ (2) 그리고[NiIII(TBDAP)(O2)]+, 의 알데하이드 디포밀레이션 반응을 살펴 본 결과, 2 의 친핵성 반응은 거대고리 리간드의 입체적 성질에 크게 의존하며, 반응성은 [NiIII(TBDAP)(O2)]+< [NiIII(CHDAP)(O2)]+ 임을 알 수 있었다. 이 결과는 구조(입체) 의 방법을 통한 근본적인 통찰력을 준다-금속-peroxo 중간체의 반응성 관계. Part II에서는, Me3-TPADP 리간드를 합성하였고 [NiII(Me3-TPADP)(CH3CN)2]2+ (3) 와 [NiIII(Me3-TPADP)(O2)]+ (4)를 준비 및 특징화하였다. 또한, 4의 반응성 결과는 외부 기질을 사용하여 얻을 수 있었다. ⓒ 2015 DGIST -
dc.description.degree Master -
dc.contributor.department Emerging materials Science -
dc.contributor.coadvisor Jeon, Won Bae -
dc.date.awarded 2015. 2 -
dc.publisher.location Daegu -
dc.description.database dCollection -
dc.date.accepted 2015-01-12 -
dc.contributor.alternativeDepartment 대학원 신물질과학전공 -
dc.contributor.affiliatedAuthor Kim, Ja lee -
dc.contributor.affiliatedAuthor Cho, Jae Heung -
dc.contributor.affiliatedAuthor Jeon, Won Bae -
dc.contributor.alternativeName 김자이 -
dc.contributor.alternativeName 조재흥 -
dc.contributor.alternativeName 전원배 -
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