Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.305803
Title: Spectroscopic and electrochemical studies of optically active bipyridyl complexes
Author: Noble, Brian Cameron
ISNI:       0000 0001 3447 9548
Awarding Body: University of Glasgow
Current Institution: University of Glasgow
Date of Award: 1987
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Abstract:
The tris(2,2'-bipyridine) complexes of ruthenium(II) and osmium(II) have been synthesised and optically resolved. The singly, doubly and triply reduced complexes have been prepared electrochemically and their circular dichroism and luminescence spectra have been measured. Investigation of the absorption, circular dichroism and luminescence spectra of the complexes and their reduced analogues strongly suggest that the added electrons are localised on the individual bipyridine ligands of the complexes. Hence the complexes are best formulated as [M(bipy)n(bipy-)3-n](n-1)+, where M = Ru, Os and n = 0, 1, 2 and 3. In addition, a chemical reduction technique using lithium metal has been developed. This has enabled the infrared spectra of the triply reduced complexes to be measured. The triply reduced ruthenium complex has been found to racemise in dry acetonitrile but is optically stable in dimethylformamide. This has been attributed to a weakening of the ligand field of bipyridine when it is reduced to the anion. Lithium 2,2'-bipyridinyl has been synthesised and complexed with the chiral co-ordinating ligands (-)-sparteine and R and S-tetra-N,N,N',N'-methyl propane-1,2-diamine whereupon its circular dichroism spectra have been measured. The tris(2,2'-bipyridine)iridium(III) complex has been synthesised and optically resolved and its hitherto unknown circular dichroism spectrum has been measured. The complex has been chemically reduced and in addition to the triply reduced complex the quadruply reduced complex has also been synthesised and their absorption and circular dichroism spectra have been measured. Investigation of the circular dichroism spectra again suggest that the added electrons are localised on the individual bipyridine ligands of the complexes.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.305803  DOI: Not available
Keywords: Physical chemistry
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