- Title
- A theoretical study of alkoxyl radical and radical cation mediated cyclisation reactions in unsaturated alkanols
- Creator
- Lee, Peter Mattison Clarke
- Subject
- Gqeberha (South Africa)
- Subject
- Eastern Cape (South Africa)
- Subject
- Density functionals
- Date Issued
- 2021-04
- Date
- 2021-04
- Type
- Doctoral theses
- Type
- text
- Identifier
- http://hdl.handle.net/10948/52130
- Identifier
- vital:43430
- Description
- A large part of this computational study focussed on selectivity patterns for 4-penten- 1-oxyl radical 1,5- and 1,6-cyclisations and for those of analogous 5-hexenyl, 4- penten-1-aminyl, 4-penten-1-iminyl and 3-phenylpropan-1-oxyl radicals. The study furthermore included cyclisation reactions of the radical cations of 4-penten-1-ol and 3-phenylpropan-1-ol. Calculations were performed for all applicable species involved in the two cyclisation modes studied, i.e. 1,5- and 1,6-cyclisation. These species included radical and radical cation precursors, as well as relevant radical transition state structures and radical adducts. All cyclisation systems investigated used the Density Functional Theory (DFT) functional B3LYP with a combination of eight basis sets. Each basis set used was a progressively higher level of theory than B3LYP/6-31G* which was used as a starting point. Cyclisations for unsubstituted species, e.g. the 4-penten-1-oxyl radical 1,5- and 1,6-cyclisations, were also simulated using the ωB97X-D and ωB97X-V functionals which account for dispersive effects. The same set of eight basis sets were used with these two functionals.
- Description
- Thesis (PhD) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Format
- computer
- Format
- online resource
- Format
- application/pdf
- Format
- 1 online resource (401 pages)
- Format
- Publisher
- Nelson Mandela University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela University
- Rights
- All Rights Reserved
- Rights
- Open Access
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