Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | 조재흥 | - |
dc.contributor.author | Hyeong Jin Youn | - |
dc.date.accessioned | 2019-10-02T16:02:19Z | - |
dc.date.available | 2019-10-02T16:02:19Z | - |
dc.date.issued | 2019 | - |
dc.identifier.uri | http://dgist.dcollection.net/common/orgView/200000171457 | en_US |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/10713 | - |
dc.description.abstract | Metal-O2 adducts, metal-superoxo, -peroxo and -hydroperoxo species, are key intermediate in metalloenzymes. Especially, metal-peroxo species plays a crucial role in the catalytic cycle of biological reaction such as aldehyde deformylation. Herein, a couple of Ni(III)-peroxo complexes, [NiIII(Me3-TPADP)(O2)]+ and [NiIII(iPr3-TPADP)(O2)]+, were synthesized by reacting Ni(II) precursor bearing N4-type tetradentate ligand (Me3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane and iPr3-TPADP = 3,6,9-triisopropyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane) with H2O2 (hydrogen peroxide) in the presence of TEA (trimethylamine) and characterized with various physicochemical methods, such as UV-vis, ESI-Master, resonance Raman and EPR. The spectroscopic and electrochemical characterization exhibits that difference of electronic properties by R groups (R = Me and iPr) is negligible. However, different steric effects of the bearing ligand are confirmed by structural analysis. In the aldehyde deformylation, the nucleophilic reactivity of the nickel(III)-peroxo complexes was highly dependent on the steric properties of the macrocyclic ligands with the reactivity order of [NiIII(iPr3-TPADP)(O2)]+ < [NiIII(Me3-TPADP)(O2)]+. | - |
dc.description.statementofresponsibility | prohibition | - |
dc.description.tableofcontents | Contents 1 Abstract 3 List of tables 4 List of figures 5 Ⅰ. Introduction Introduction 8 II. Experimental section 2.1 Materials and Instrumentation 9 2.2 Synthesis 11 2.2.1 Me3-TPADP 11 2.2.2 iPr3-TPADP 12 2.2.3 [Ni(Me3-TPADP)(NO3)](NO3) 13 2.2.4 [Ni(iPr3-TPADP)(NO3)](NO3) 13 2.2.5 [Ni(Me3-TPADP)Cl2] 14 2.2.6 [Ni(iPr3-TPADP)Cl2] 15 2.3 Magnetic measurement 16 2.4 X-ray crystallography 17 2.5 Reactivity 20 III. Results and discussion 3.1 Synthesis and Characterization of Nickel(II) starting complexes 21 3.2 Synthesis and Characterization of Nickel(III)-Peroxo complexes 24 3.3 Reactivity 31 3.4 Comparison of Steric Effect between 3 and 4 36 IV. Conclusion 4.1 Conclusion 38 |
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dc.format.extent | 45 | - |
dc.language | eng | - |
dc.publisher | DGIST | - |
dc.source | /home/dspace/dspace53/upload/200000171457.pdf | - |
dc.title | Spectroscopic Characterization and Reactivity Study of Nickel-Peroxo Species | - |
dc.type | Thesis | - |
dc.identifier.doi | 10.22677/thesis.200000171457 | - |
dc.description.degree | MASTER | - |
dc.contributor.department | Emerging Materials Science | - |
dc.contributor.coadvisor | Hochun Lee | - |
dc.date.awarded | 2019-02 | - |
dc.publisher.location | Daegu | - |
dc.description.database | dCollection | - |
dc.citation | XT.MM 윤94 201902 | - |
dc.date.accepted | 2019-01-30 | - |
dc.contributor.alternativeDepartment | 신물질과학전공 | - |
dc.embargo.liftdate | 2024-01-01 | - |
dc.contributor.affiliatedAuthor | Lee, Hochun | - |
dc.contributor.affiliatedAuthor | Cho, Jaeheung | - |
dc.contributor.affiliatedAuthor | Youn, Hyeong Jin | - |
dc.contributor.alternativeName | 윤형진 | - |
dc.contributor.alternativeName | 이호춘 | - |
dc.contributor.alternativeName | Jaeheung Cho | - |
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