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Title: Some cluster chemistry of ruthenium
Author: Shephard, Douglas Stuart
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1996
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This thesis describes research directed towards the synthesis, full chemical, spectroscopic and structural characterisation, and reactivity in selected cases of some ruthenium carbonyl clusters containing both π-donor and σ-donor ligands. Cluster nuclearities range between three and six metal atoms and are shown to display a variety of core geometries. Discussions centred on C-H and C-C activation, redox behaviour., magnetic susceptibility, solid state chemistry, mechanism and supramolecular chemistry are all presented. Chapter one contains some highlights of modern cluster chemistry and pays particular attention to redox, magnetic and C-H activation properties of clusters. The area of materials science is also touched upon in conjunction with the potential input from the cluster chemist. Chapter two describes the synthesis and characterisations of a range of compounds wherein a cluster moiety is bound to an extended polycyclic hydrocarbon framework, with a view to their incorporation into organometallic materials. Chapter three introduces the 'pseudo' arene fulvene in respect to its bonding interactions with clusters. A wide variety of compounds are presented isolated from substitution reactions with the parent cluster carbonyls. Chapter four introduces the concept of linking redox active clusters to a second redox active centre. The redox active centres chosen are based on ferrocene and cobaltocene and linked to the clusters by phosphine groups. Novel magnetic behaviour and reactivity has been observed in these systems. Chapter five contains a varied set of compounds which are essentially collections of clusters bound to more exotic π-donor ligands. This work focuses on the use of functional groups such as carboxylates and macrocycles for polymer precursors or host compounds or to give chirality to the cluster bound fragment. Chapter six presents the experimental details of the various methods of synthesis and characterisation used. It also contains spectroscopic and solid state data of the compounds.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available