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Spectroscopic Characterization and Reactivity Study of Nickel-Peroxo Species

Title
Spectroscopic Characterization and Reactivity Study of Nickel-Peroxo Species
Authors
Hyeong Jin Youn
DGIST Authors
Youn, Hyeong Jin; Lee, Hochun; Cho, Jaeheung
Advisor(s)
조재흥
Co-Advisor(s)
Hochun Lee
Issue Date
2019
Available Date
2019-10-03
Degree Date
2019-02
Type
Thesis
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)]+.
Table Of Contents
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
URI
http://dgist.dcollection.net/common/orgView/200000171457
http://hdl.handle.net/20.500.11750/10713
DOI
10.22677/thesis.200000171457
Degree
MASTER
Department
Emerging Materials Science
University
DGIST
Related Researcher
  • Author Lee, Hochun Electrochemistry Laboratory for Sustainable Energy(ELSE)
  • Research Interests Lithium-ion batteries; Novel Materials for rechargeable batteries; Novel energy conversion;storage systems; Electrochemistry; 리튬이차전지; 이차전지용 신규 전극 및 전해액; 신규 에너지변환 및 저장 시스템; 전기화학
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Department of Emerging Materials ScienceThesesMaster


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