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Title: The design of coinage metal and pnictogen architectures
Author: Stonor, Andrew James
ISNI:       0000 0004 5918 1723
Awarding Body: University of Bristol
Current Institution: University of Bristol
Date of Award: 2015
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A series of experiments were designed with the dual goals of, firstly, accessing new pnictogen ring and cage architectures suitable for use as antiwear additives in industrial lubricants and, secondly, to synthesise novel coinage metal complexes utilising both organic and inorganic ligands. Several asymmetrically and symmetrically substituted cyclodiphosphazanes were synthesised and in the majority of cases the cisoid or transoid isomerism was determined in solution by 31p NMR spectroscopy. Moreover, in three cases the molecular structures of cyclodiphosphazanes were examined using X-ray crystallography. Exo,exo-diamino- and amido-phosphorus sesquisulfide compounds were also characterised by 31p NMR spectroscopy which revealed phosphorus sesquisulfide itself as a decomposition product too. 31p NMR spectroscopy was also used to identify the presence of two new metalphosphorus sesquisulfide coordination species in which the inorganic cage acts as a ditopic ligand via coordination from phosphorus and a rare example of sulfur coordination. Selected cyclodiphosphazanes and phosphorus sulfides were also blended with industrial lubricant (group 1 base oil) and subject to antiwear and friction modifying tests. Furthermore, the structures of fifteen organometallic group 11 metal complexes using alkenes, dienes, trienes, arenes, alkynes and isonitriles as ligands were elucidated using X-ray crystallography, the parameters of which, were compared to analogous and similar examples reported in the literature. These compounds were further characterised by multinuclear NMR spectroscopy, IR spectroscopy and elemental analysis, the former of which provided evidence for the behaviour of complexes in solution.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available