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The electrochemical oxidation of mercury (II) - Olefin complexes

The electrochemical oxidation of mercury (II) - Olefin complexes
The electrochemical oxidation of mercury (II) - Olefin complexes
It has been known for many years that acidic solutions of mercuric ions absorb olefins rapidly to form o bonded complexes. The eloctro- chemical. oxidation of eleven such complexes (those of ethylene, propena, but-1-ane, but-2-ene, pent-l-ene, pent-2-ene, hex-l-ena, hex-2-ene, oct-1-ene, isobutane and cyclohexene) is reported. The high solubility of these mercury(II) - olefin complexes allows concentrated aqueous solutions of olefins to be msde so that the oxidation can be carried out at high current densities. The electrode reaction is the first reported example of an electrochemical oxidation of a complex resulting in the fission of a metal-carbon bond thus regenerating the mercuric ion. The mercuric ion can, therefore, be regarded as a catalyst since the complex may be readily regenerated by bubbling olefin through the solution. The effect of pH (for the propene ccmplex) and of electrode potential (for the propene, but-1-ene and but-2-ene complexes) on the products of the reaction was investigated. The products of the oxidation of the complexes of eleven olefins were determined at one fixed potential. The principal products which are found are carboxylic acids, together with small amounts of aldehydes and ketones which, it is shown, are probably the first products of the electrode reaction. A mechanicm which involves the rearrangement of a carbonium ion has been suggested for the reaction. The carbonium ion can rearrange either by an alkyl or a hydride shift and the ratio of products formed via these two routes has been shown to depend on the size of the migrating group and, for propene, on the anion present. Values of the ratio of alkyl to hydride shift were obtained for several alkyl groups and the relative alkyl to alkyl shift ratios calculated from these are compared with values in the literature.
University of Southampton
Race, George
c8f36a4c-82e0-4485-8be6-32b1729292ac
Race, George
c8f36a4c-82e0-4485-8be6-32b1729292ac
Pletcher, Derek
f22ebe69-b859-4a89-80b0-9e190e6f8f30

Race, George (1970) The electrochemical oxidation of mercury (II) - Olefin complexes. University of Southampton, Doctoral Thesis, 113pp.

Record type: Thesis (Doctoral)

Abstract

It has been known for many years that acidic solutions of mercuric ions absorb olefins rapidly to form o bonded complexes. The eloctro- chemical. oxidation of eleven such complexes (those of ethylene, propena, but-1-ane, but-2-ene, pent-l-ene, pent-2-ene, hex-l-ena, hex-2-ene, oct-1-ene, isobutane and cyclohexene) is reported. The high solubility of these mercury(II) - olefin complexes allows concentrated aqueous solutions of olefins to be msde so that the oxidation can be carried out at high current densities. The electrode reaction is the first reported example of an electrochemical oxidation of a complex resulting in the fission of a metal-carbon bond thus regenerating the mercuric ion. The mercuric ion can, therefore, be regarded as a catalyst since the complex may be readily regenerated by bubbling olefin through the solution. The effect of pH (for the propene ccmplex) and of electrode potential (for the propene, but-1-ene and but-2-ene complexes) on the products of the reaction was investigated. The products of the oxidation of the complexes of eleven olefins were determined at one fixed potential. The principal products which are found are carboxylic acids, together with small amounts of aldehydes and ketones which, it is shown, are probably the first products of the electrode reaction. A mechanicm which involves the rearrangement of a carbonium ion has been suggested for the reaction. The carbonium ion can rearrange either by an alkyl or a hydride shift and the ratio of products formed via these two routes has been shown to depend on the size of the migrating group and, for propene, on the anion present. Values of the ratio of alkyl to hydride shift were obtained for several alkyl groups and the relative alkyl to alkyl shift ratios calculated from these are compared with values in the literature.

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Published date: 1 October 1970

Identifiers

Local EPrints ID: 437515
URI: http://eprints.soton.ac.uk/id/eprint/437515
PURE UUID: a08157f8-5343-445a-aacb-a4e42f20c17e

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Date deposited: 03 Feb 2020 17:31
Last modified: 25 Mar 2020 17:30

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Contributors

Author: George Race
Thesis advisor: Derek Pletcher

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