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Title: Organometallic chemistry of triosmium clusters
Author: Nairn, Jacqueline G. M.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1995
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The interaction of transition metal carbonyl clusters with unsaturated cyclic and polycyclic ligand systems continues to stimulate ongoing research and this thesis is concerned mainly with the reactions of triosmium carbonyl clusters with such compounds. Chapter one contains a brief summary of triosmium dodecacarbonyl chemistry, incorporating both synthesis and reactivity. The arene chemistry of mononuclear complexes and cluster compounds is also discussed. Over the last decade there has been serious debate on the validity of the cluster-surface analogy; the boundary conditions are addressed herein. Chapter two details alternative synthetic routes to the compound M3(CO)9(μ-η2.2..2-C6H6) [M = Ru, Os]. A series of substituted 1,3-cyclohexadiene ligands have also been prepared and reacted with the cluster Os3(CO)10(MeCN)2. The successful synthesis of the bis-benzene cluster Os3(CO)63-η2.2.2.-C6H6)(η6-C6H6) is reported in chapter three. The systematic stepwise reaction of Os3(CO)932.2.2-C6H6) with trimethylamine-N-oxide and 1,3-cyclohexadiene leads to the formation of a range of benzene-diene clusters, all of which have been fully characterised. Their isomeric and fluxional behaviour has also been studied. The reactions of acenaphthylene, C12H8, a stable tricyclic system with 12 π-electrons available for bonding, are reported for Ru3(CO)12 and Os3(CO)12 in chapter four. The resulting compounds demonstrate the range of bonding modes adopted by this flexible ligand.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available