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Title: Synthesis and characterisation of novel, redox-active complexes of ruthenium and osmium
Author: Horsburgh, Lockhart E.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1994
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This thesis reports the synthesis and characterisation of a number of novel complexes of Ru and Os. The complexes studied all have more than one redox centre. A major objective of this research was investigation of the redox behaviour of the complexes formed, primarily by electrochemical and in situ spectroelectrochemical studies. In chapter 1 the electrochemical and in situ spectroelectrochemical techniques employed during this work are discussed. Chapters 2 and 3 report reactions of tetracyanoethylene (tcne) and tetracyanoquinodimethane (tcnq) with various complexes of Ru and Os. In the vast majority of cases tcnx (x = e or q) was found to coordinate to the metal centre via nitrogen. Electrochemical and spectroelectrochemical studies were employed to elucidate the nature of the frontier orbitals. In general the complexes exhibited facile ligand-based reductions while oxidative processes were metal-based. In chapter 2 reactions of tcnx with cis-Ru(bpy) 2C12 (bpy = 2,2'-bipyridyl), and electrochemically induced reactions of tcne with [OsC16]2-, [OsBr6]2- and [OsC15(py)]- (py = pyridine) are reported. Chapter 3 discusses reactions of tcnx with phosphine complexes of Ru and Os. Of particular interest was the formation of trans-[OsC12(PEt2Ph) 3{(NC)2C=C(OH) (CN)}, the first reported example of metal-bound tricyanovinyl alcohol. In addition to studies of the redox processes, the mechanism of formation of the above complex was investigated. Chapter 4 discusses trinuclear mixed valence complexes of general formula XL2Ru(μ-X) 3Ru(μ-X)3RuL2X, where X = C1 or Br and L is a tertiary phosphine or arsine. In particular the nature of the metal-metal interactions was investigated, primarily by single crystal X-ray diffraction, electrochemistry and spectroelectrochemistry. The results obtained are generally consistent with Ru-Ru bonding and extensive delocalisation of the metal-based valence electrons.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available