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A Mononuclear Side-on Peroxocobalt(III) Complex in Nitrile Activation

Title
A Mononuclear Side-on Peroxocobalt(III) Complex in Nitrile Activation
Authors
Noh, Hyeon Ju
DGIST Authors
Noh, Hyeon Ju; Cho, Jae Heung; Koo, Jae Hyung
Advisor(s)
Cho, Jae Heung
Co-Advisor(s)
Koo, Jae Hyung
Issue Date
2017
Degree Date
2017. 2
Type
Thesis
Keywords
Peroxocobalt(III) complexHydroximatocobalt(III) complexNitrile activation코발트 퍼옥소나이트릴 활성화하이드록시메이토코발트프로드러그
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
Table Of Contents
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 --
URI
http://dgist.dcollection.net/jsp/common/DcLoOrgPer.jsp?sItemId=000002322258
http://hdl.handle.net/20.500.11750/1492
DOI
10.22677/THESIS.2322258
Degree
Master
Department
Emerging materials Science
University
DGIST
Files:
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Collection:
Emerging Materials ScienceThesesMaster


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