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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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