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Title: Functionalised transition metal clusters of cobalt and osmium
Author: Brown, Alisdair James
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1995
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In Chapter One, a review of the chemistry of the tricobalt nonacarbonyl methylidyne cluster is presented. The concept of organic polymeric species containing inorganic moieties is introduced and methods of synthesis and characterisation are discussed. The importance of these compounds as potentially homogenised heterogeneous catalysts is highlighted, and some examples of these species are given. Finally, the catalytic cross linking of alkyd polymers is considered. In the second chapter, the synthesis and characterisation of some tricobalt clusters and their derivatives is presented. Reaction of [(CO)9Co33-CCO)]+ [AlCl4-] with nucleophiles ROH produced the compounds [(CO)9Co33-CCOOR)], where R= CH2CH=CH2 (1) and CH2CH2O(CO)CH=CH2 (2). The crystal structure of (1) is presented, and whilst it does not undergo polymerisation, compound (2) is readily polymerised by free radical initiation in both solution and emulsion systems with acrylic comonomers. The polymeric systems were characterised by infrared and ultra violet spectroscopy, as well as by gel permeation chromatography. However, neither the polymeric or monomeric cluster systems were found to catalyse the cross linking of alkyd polymers as they exhibit no redox properties under the ambient conditions studied. Chapter Three describes the synthesis and characterisation of triosmium clusters which contain functionalised alkynes. The crystal structure of [Os3(CO)8(μ-CO)(HOCH2C=CCHOCCHCCH2) is reported. Attempts to make polymeric and multicluster derivatives of these functionalised compounds are described. Chapter Four details the synthesis and characterisation of a novel amide linked di-cluster. Reaction of [(CO)9Co33-CCO+)][PF6-] with [(CO)9Co33-C)(p-C6H4NH2)] produced the species [(CO)9Co33-CCON(H)-p-C6H43-CCo3(CO)9], which has been characterised by X Ray crystallography, as well as by IR, NMR, FABMS and electrochemical techniques.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available