Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Cho, Jae Heung | - |
dc.contributor.author | Noh, Hyeon Ju | - |
dc.date.accessioned | 2017-05-10T08:53:27Z | - |
dc.date.available | 2020-02-28T09:21:29Z | - |
dc.date.issued | 2017 | - |
dc.identifier.uri | http://dgist.dcollection.net/jsp/common/DcLoOrgPer.jsp?sItemId=000002322258 | en_US |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/1492 | - |
dc.description.abstract | Oxidation processes mediated by metal-oxygen adducts have attracted much attention in biomimetic and enzymatic reactions. Although a number of metal-oxygen species has been prepared and investigated in oxidation reactions toward diverse organic substrates under mild conditions, activation of nitriles has rarely been examined in oxidation process of metal-oxygen complexes. Herein, we report the first example of nitrile activation by a side-on peroxocobalt(III) complex with a tetradentate macrocyclic ligand. The peroxocobalt(III) complex is capable of performing nitrile activation of CH3CN to give a mononuclear hydroximatocobalt(III) complex where the nitrile is oxidized by two oxygen atoms of the peroxo group. 18O labeling experiments indicate dioxygenase-like reactivity of the peroxocobalt(III) complex in nitrile activation. Such an unprecedented nitrile activation was confirmed by the activation of other nitrile compounds (e.g., CH3CH2CN and C6H5CN), which gives corresponding hydroximatocobalt(III) complexes. Kinetic studies including the Hammett analysis and isotope labeling experiments proposed that the nitrile activation occurs via a concerted mechanism. These results will expand the range of nitrile activation processes. ⓒ 2017 DGIST | - |
dc.description.tableofcontents | Ⅰ. Introduction-- 1.1 Motivation 1-- 1.2 Previous works 1-- 1.3 This work 2-- II. Experimental section-- 2.1 Materials and Instrumentation 2-- 2.2 Synthesis 4-- 2.2.1 [Co(TBDAP)(NO3)(H2O)](NO3) 4-- 2.2.2 [Co(TBDAP)(O2)](NO3) (1-NO3∙2H2O) 4-- 2.2.3 [Co(TBDAP)(CH3C(O)NO)](NO3)(H2O) (2-NO3∙H2O) 5-- 2.2.4 [Co(TBDAP)(CH3CH2C(O)NO)](NO3) (3-BPh4) 5-- 2.2.5 [Co(TBDAP)(C6H5C(O)NO)](BPh4) (4-BPh4∙H2O) 6-- 2.3 Magnetic measurement 6-- 2.4 X-ray crystallography 7-- 2.5 Reactivity 13-- III. Results and discussion-- 3.1 Synthesis and Characterization of Cobalt(III)-peroxo complex 13 -- 3.2 Synthesis and Characterization of Hydroximatocobalt(III) complexes 23-- 3.3 Reactivity 30-- IV. Conclusion-- 4.1 Conclusion 32 -- |
- |
dc.format.extent | 37 | - |
dc.language | eng | - |
dc.publisher | DGIST | - |
dc.subject | Peroxocobalt(III) complex | - |
dc.subject | Hydroximatocobalt(III) complex | - |
dc.subject | Nitrile activation | - |
dc.subject | 코발트 퍼옥소 | - |
dc.subject | 나이트릴 활성화 | - |
dc.subject | 하이드록시메이토코발트 | - |
dc.subject | 프로드러그 | - |
dc.title | A Mononuclear Side-on Peroxocobalt(III) Complex in Nitrile Activation | - |
dc.type | Thesis | - |
dc.identifier.doi | 10.22677/THESIS.2322258 | - |
dc.description.alternativeAbstract | 본 논문은 코발트 퍼옥소 종에서 일어나는 나이트릴 활성화에 관한 것이다. 생체 내에 있는 금속 효소는 산소와 같은 작은 분자들을 활성화 시켜 자연계에 존재하는 물질을 생체 전환시키거나 산화적 대사, 인산화와 같은 다양한 반응을 일으킨다. 따라서 효소들의 생체 내 작용 기전에 대한 연구를 위하여 새로운 코발트 모델 화합물을 합성하였고 산소의 활성화를 통한 반응 중간체인 코발트-퍼옥소 종을 합성하였다. 또한 이전에 없던 금속-산소 종에서의 나이트릴 활성화 반응을 통하여 하이드록시메이토 코발트 (hydroximatocobalt(III)) 화합물을 합성하였다. 본 논문에서는 아세토나이트릴(acetonitrile), 프로피오나이트릴(propionitrile), 벤조나이트릴(benzonitrile)을 이용하여 다양한 나이트릴 화합물에서의 활성화 반응을 통하여 각 나이트릴 화합물에 대한 하이드록시메이토 코발트 화합물을 합성하였다. 하이드록삼산(hydroxamic acid)은 금속효소의 저해제로 잘 알려져 있으며 암 치료제, 알츠하이머 치료제 개발에 대한 연구가 진행되어 왔다. 본 논문의 하이드록시메이토 코발트 화합물은 다양한 나이트릴 유도체를 사용하여 다양한 하이드록삼산 유도체가 배위된 형태를 합성할 수 있어 프로드러그(prodrug) 연구에 큰 의의를 가진다. ⓒ 2017 DGIST |
- |
dc.description.degree | Master | - |
dc.contributor.department | Emerging materials Science | - |
dc.contributor.coadvisor | Koo, Jae Hyung | - |
dc.date.awarded | 2017. 2 | - |
dc.publisher.location | Daegu | - |
dc.description.database | dCollection | - |
dc.date.accepted | 2017-01-18 | - |
dc.contributor.alternativeDepartment | 대학원 신물질과학전공 | - |
dc.contributor.affiliatedAuthor | Noh, Hyeon Ju | - |
dc.contributor.affiliatedAuthor | Cho, Jae Heung | - |
dc.contributor.affiliatedAuthor | Koo, Jae Hyung | - |
dc.contributor.alternativeName | 노현주 | - |
dc.contributor.alternativeName | 조재흥 | - |
dc.contributor.alternativeName | 구재형 | - |
There are no files associated with this item.