Synthesis of New Perfluoropropenyl Organometallic Compounds

Abstract

In the last 50 years, fewer than 35 perfluoropropenyl organometallic complexes have been published. Therefore, the first part of this thesis focuses on the synthesis and investigation of new perfluoropropenyl organometallic compounds, using Z-HFC-1225ye (CF3CF=CFH) as the starting material along with a suitable metalhalide or silicon-halide. Several new transition metal perfluoropropenyl complexes (Au, Pd, Ti, Pt) and silicon-perfluoropropenyl compounds were successfully synthesised and characterised via multinuclear NMR and IR spectroscopy, X-ray crystallography and elemental analysis. The second part of the thesis focuses on assessing these compounds reactivity and chemistry. The assessment included palladium-catalysed reactions, with the aim of forming new C-C bonds by Stille and Hiyama cross-coupling; substitution reactions using an organolithium reagent (nBuLi, tBuLi, MeLi, and PhLi), which successfully substituted one fluorine within the perfluoropropenyl group. This resulted in the formation of a mixture of two isomers R4-nSi(Z-CF=CRCF3)n and R4-nSi(E-CR=CFCF3)n, and reactions using lithium aluminium hydride to form compounds of the type R4-nSi(CH=CHCF3)n. The final part of the project focused on investigating HFC-1234yf (CH2=CFCF3) and E-HFC-1234ze (CF3CH=CFH) as potential sources for derivatives of the perfluoropropenyl system.

Date of Award	31 Dec 2018
Original language	English
Awarding Institution	The University of Manchester
Supervisor	Alan Brisdon (Supervisor) & Robin Pritchard (Supervisor)