Electrochemical reduction of fluorinated systems and derived chemistry

Abstract

The work described in this thesis is divided into four sections:1. The electrochemical reduction of fluorocarbon derivatives has been investigated. A number of systems have been studied analytically (using cyclic volt amine try) ; whilst preparatively a range of compounds have been synthesised, including semi-conducting polymers and four-memberedperfluorocyclic products. 2. The use of sodium amalgam as an electromimetic medium to facilitate reduction of various fluorocarbon substrates has been studied. A series of volatile cyclic and acyclic F-dienes have been prepared from F-alkenes in good yield and conversion. The chemistry of these F-dienes is then described: 3. Both mono- and bi- functional nucleophiles have been reacted, giving a range of novel substitution products. 4. A number of free radical and cycloaddition reactions have been attempted without success. However, the complexation of decamethylferrocene as a metallocene one electron donor, with various F-alkenes of low reduction potential, has allowed a radical anion of a perfluorocyclic-diene to be stabilized and fully characterized for the first time.