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Title: Electrochemical and spectroelectrochemical studies on mixed halo/pyridine osmium complexes
Author: Taylor, Kenneth John
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1990
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The complexes [OsCl6-nPYn](n-y)+ , where n = 0, 1, 2(trans), 2(cis), 3(mer), 4(trans), 5 and 6, and y varies between 2 and 4, have been synthesised via redox induced substitution reactions of [OsCl6]2-. The series has been fully characterised using electrochemical and spectroelectrochemical techniques. Several key members namely trans-[TPA] [OsCl4py2], cis-[OsCl4py2], trans-[OsCl2py4] and [Ospy6]9BF4]2, have also been examined by X-ray crystallography. Voltammetric data derived from these complexes has been compared to PROB*LEM/2 values predicted by two recent models. PROB*LEM/2 values for the series [OsCl6-nPYn](n-y), where y = 3 and 2, are dependent on n but independent of the isomeric form adopted. However, we propose that PROB*LEM/2 values for the series [OsCl6-nPYn](n-4)+ are dependent not only on n and the isomeric form, but also on the precise coordination mode of the pyridine ligands. As a comparison some members of the series [OsBr6-npyn](n-y)+ and [OsI6-npyn](n-y)+ , and complexes [TBA][OsCl5L], where L = PhCn, 2, 3 and 4-cyanopyridine and 3,4-dicyanopyridine, have also been synthesised and characterised using the methods described above. Kinetic studies on the reduction of [OsCl6]2- in the presence of pyridine, dmf and CO suggest Cl- loss is the rate determining step for this process.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available