The synthesis and characterisation of novel fluorinated compounds suitable for evaluation as oil additives

A review of the history, development and application of lubricant additives in mineral oils is presented, along with recent developments in base fluids leading to need for fluorous phase soluble compounds in this area. The experimental work illustrated in this thesis describes the synthesis of a series of perfluoroalkyl-derivatised dithiophosphate (Rf = (CH2)2C6F 13, (CH2)2C4F9, (CH 2)3CF3) (1) and xanthate (Rf = (CH 2)2C6F13, (CH2)2C 4F9, (CH2)3C8F17, (CH2)3C6F13, (CH2) 3CF3) (2) ligands and closely related perprotio analogues (RH = C8H17), which have been analysed by 1H, 19F and 31P{lcub}1H{rcub} NMR spectroscopy, mass spectroscopy and elemental analysis. The influence of the electronic properties of the perfluoroalkyl groups have been investigated in a study of the co-ordination chemistry of these ligands to a range of transition metal centres including [(PPh3)2CuL], [Cp*RhClL], [NiL 2] and [ZnL2]. (Fig. 3751) The complexes have been analysed using a variety of techniques including multi-nuclear NMR spectroscopy, mass spectrometry, X-ray crystallography and elemental analysis. The anti-wear and extreme pressure properties of a selected number of compounds formed have been evaluated using industry standard SRV testing procedures, allowing a direct comparison of the perfluoroalkyl-derivatised complexes with their perprotio congeners. Preliminary work is also described on the formation of perfluoroalkyl-derivatised dithiocarbamate and phenate compounds, which could also potentially find applications within the lubricant industry as anti-wear and detergent additives respectively.