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Title: Synthesis and characterisation of palladium and platinum complexes of chalcogen-containing ligands
Author: Lewtas, M. R.
Awarding Body: University of Wales Swansea
Current Institution: Swansea University
Date of Award: 2000
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The thesis contains reviews of the chemistry of transition metal polychalcogenides, the characterisation, properties and uses of transition metal dithiolenes and the synthetic history, characterisation and properties of transition metal diselenolenes. There are also reviews of the synthesis, characterisation and properties of dimers and trimers of the nickel triad containing phosphine ligands and two bridging chalcogenide atoms, the synthesis and characterisation of nickel triad polychalcogenides and transition metal ditelluorlenes. Other literature described concerns phosphine substituted dithiolene and diselenolene complexes of the nickel triad and the synthesis of transition metal diselenolenes from 1, 2, 3-selenadiazoles. The reactions of bis[bis(diphenylphosphino)ethane]palladium and -platinum with elemental chalcogens are described. Reaction of bis[bis(diphenylphosphino)ethane]platinum with elemental selenium in toluene under reflux, or of [bis(diphenylphosphino)ethane]dichloroplatinum with lithium polyselenide in tetradhydrofuran, led in good yield to the complex [bis(diphenylphosphino)ethane]-(tetraselenido-Se, Se)platinum whose structure was determined by X-ray crystallography. Reaction of bis[bis(diphenylphosphino)ethane]platinum with elemental tellurium, followed by treatment with dichloromethane led to isolation of the salt tris[bis(diphenylphosphino)ethane]di-μ3-telluridotriplatinum dichloride. Bis[bis(diphenylphosphino)ethane]palladium reacted with elemental selenium to give bis[bis(diphenylphosphino)ethane]di-μ2-selenidodipalladium or tris[bis(diphenylphosphino)ethane]di-μ3-selenidotripalladium dichloride depending on the conditions. The reactivity of palladium and platinum chalcogenide complexes containing dppe towards various activated alkynes was examined. The tetrachalcogenides [bis(diphenylphosphino)ethane](tetrasulphido-S, S)palladium, -platinum and [bis(diphenylphosphino)ethane](tetraselenido-Se, Se)platinum reacted with the activated alkynes dimethyl- and diethylacetylenedicarboxylate to form dithiolenes and diselenolenes such as [bis(diphenylphosphino)ethane]bis(ethoxycarbonyl)ethene-1,2-(diselenolato-Se, Se)]platinum.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available