DGIST Scholar: The Oxygen Rebound Mechanism of C-H Bond Oxidation Reaction by Non-Heme Manganese-Oxygen Species

Title: The Oxygen Rebound Mechanism of C-H Bond Oxidation Reaction by Non-Heme Manganese-Oxygen Species

Citation: Lee, Yujeong. (2020). The Oxygen Rebound Mechanism of C-H Bond Oxidation Reaction by Non-Heme Manganese-Oxygen Species. doi: 10.22677/thesis.200000321130

Description: Manganese(IV)–hydroxo complex, C–H bond activation, Oxygen non-rebound mechanism

Abstract: A high-valent manganese–hydroxo complex has been synthesized and characterized using various physicochemical methods such as UV–vis, ESI-MS, IRPD, and DFT calculations. Generally, manganese-oxygen adducts can activate C–H bond through an oxygen non-rebound mechanism where the rate of hydrogen atom transfer (HAT) depends on the strength of C–H bond. Herein, in the formation process of manganese–hydroxo complex, [MnIV(CHDAP–O)(OH)]2+, the C–H bond activation of the 2,6 position in cyclohexyl groups unusally proceeds via an oxygen rebound mechanism, in which HAT is identified as a rate determining step.
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Table Of Contents: Contents
Abstract i
List of contents iii
List of figures iv
List of tables vi

I. Introduction

II. Experimental section
2.1 Materials and Instrumentation 2
2.2 Synthesis 3
2.2.1 A deuterated CHDAP ligand 3
2.2.2 [MnII(CHDAP)(OTf)2] 5
2.2.3 [MnIV(CHDAP–O)(OH)]2+ 6
2.3 X-ray crystallography 6

III. Results and discussion

3.1 Preparation and Characterization of a Deuterated CHDAP Ligand 10
3.2 Synthesis and Characterization of a Manganese(II)-Starting Complex 12
3.3 Synthesis and Characterization of a Manganese(IV)–Hydroxo Complex 15
3.4 The Effect of the Deuterium Exchange in the 2,6 Position of Cyclohexyl Groups 20
3.5 Consideration 27

IV. Conclusion

List of figures

URI: http://dgist.dcollection.net/common/orgView/200000321130
http://hdl.handle.net/20.500.11750/12179

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