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
- Author(s)
- Lee, Yujeong
- DGIST Authors
- Lee, Yujeong ; Cho, Jaeheung ; Lee, Sunggi
- Advisor
- 조재흥
- Co-Advisor(s)
- Lee, Sunggi
- Issued Date
- 2020
- Awarded Date
- 2020/08
- Type
- Thesis
- 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.
- 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
- Degree
- Master
- Department
- Department of Emerging Materials Science
- Publisher
- DGIST
- Related Researcher
-
-
Lee, Sunggi
- Research Interests Organic synthesis; Catalyst development; Reaction development; Radical chemistry; Stereoselective reaction
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- Appears in Collections:
- Department of Physics and Chemistry Theses Master
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