The deposition and chemistry of manganese and zinc in non-aqueous solutions
The deposition and chemistry of manganese and zinc in non-aqueous solutions
The electrodeposition of manganese and zinc from non-aqueous solvents was investigated using microelectrodes. Good quality data, free from iR distortion was obtained. Zinc deposition from ZnBr2/TBABF4/THF was found to be simple and rapid. The deposition process proved to be completely reversible.
Manganese deposition from three distinct systems was also investigated, i.e., MnBr2/TBABF4/THF, MnBr2/LiBr/THF and MnBr2/TBABF2/TBABF4/DMF. In all cases the deposition reaction proved to be complex and not completely reversible. Analysis of the deposits formed showed that they contained large amounts of some `MnBr' species. It was found that in all the above cases nucleation was instantaneous and was followed by three dimensional growth which was under electron transfer control.
The synthesis and reactions of organomanganous reagents was also studied. Manganese alkyls, synthesised from BuLi and MnBr2, were found to react selectively with acid chlorides to give good ketone yields under relatively mild conditions. The solvent and choice of organomanganous species were found to be very important.
Organomanganous reagents were also synthesised directly using manganese powder. A Reformatsky type reaction was carried out where an organomanganous species synthesised by reaction of manganese powder with ethyl bromoacetate, was reacted with benzaldehyde. Relatively good yields of the β-acetoxy ester product were obtained, although it was evident that side reactions were occurring.
University of Southampton
1993
Gonsalves, Marylou
(1993)
The deposition and chemistry of manganese and zinc in non-aqueous solutions.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The electrodeposition of manganese and zinc from non-aqueous solvents was investigated using microelectrodes. Good quality data, free from iR distortion was obtained. Zinc deposition from ZnBr2/TBABF4/THF was found to be simple and rapid. The deposition process proved to be completely reversible.
Manganese deposition from three distinct systems was also investigated, i.e., MnBr2/TBABF4/THF, MnBr2/LiBr/THF and MnBr2/TBABF2/TBABF4/DMF. In all cases the deposition reaction proved to be complex and not completely reversible. Analysis of the deposits formed showed that they contained large amounts of some `MnBr' species. It was found that in all the above cases nucleation was instantaneous and was followed by three dimensional growth which was under electron transfer control.
The synthesis and reactions of organomanganous reagents was also studied. Manganese alkyls, synthesised from BuLi and MnBr2, were found to react selectively with acid chlorides to give good ketone yields under relatively mild conditions. The solvent and choice of organomanganous species were found to be very important.
Organomanganous reagents were also synthesised directly using manganese powder. A Reformatsky type reaction was carried out where an organomanganous species synthesised by reaction of manganese powder with ethyl bromoacetate, was reacted with benzaldehyde. Relatively good yields of the β-acetoxy ester product were obtained, although it was evident that side reactions were occurring.
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Published date: 1993
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Local EPrints ID: 462511
URI: http://eprints.soton.ac.uk/id/eprint/462511
PURE UUID: 0faa5e17-ab82-495c-a002-60d3d5f6589e
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Date deposited: 04 Jul 2022 19:10
Last modified: 04 Jul 2022 19:10
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Author:
Marylou Gonsalves
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