Date of Award


Degree Type


Degree Name

Doctor of Philosophy


This thesis describes the preparation, characterisation, and reactivity of a new class of platinacyclobutane complexes, containing a hydroxyl or ester functionality. The monomeric compounds are prepared by the reaction of Zeise's dimer with the appropriate cyclopropane derivative and subsequent addition of pyridine.;Owing to the presence of the hydroxyl group, these complexes have been shown to interact with the shift reagent, Eu(fod)(,3), so as to greatly simplify their ('1)H-N.M.R. spectra. Using the results obtained from this study and the equation of Karplus, comparisons are drawn between ring conformations in the solid state and solution which indicate significant puckering of these complexes in solution.;A novel ring expansion reaction is presented by which platinacyclopentanes are prepared by solvolysis of the platinacyclobutylcarbinyl esters, under mild conditions. Platinacyclopentanes are the exclusive products, identified by their ('13)C and ('1)H N.M.R. spectra. The mechanism by which this rearrangement proceeds was studied by kinetics as well as suitable ('13)C and ('2)H labelling studies in the absence and presence of added pyridine. The results indicate one overall mechanism with a step dependent on pyridine concentration.;The reactions of Zeise's dimer with bicyclo{lcub}2.1.0{rcub}pentane and quadricyclane, in acetone, are shown to give cyclopentene and norbornadiene (NBD) and {lcub}PtCl(,2)((mu)-Cl)(,2)(cyclopentene)(,2){rcub} and {lcub}PtCl(,2)(NBD){rcub} as the respective products.;1-Methylcyclopropyl carbinol and 2-cyclopropyl-2-propyl-p-nitrobenzoate react cleanly, in acetone, with {lcub}Rh(,2)Cl(,2)(CO)(,4){rcub} to gibe 1-methylcyclobutanol and 5-chloro-2-pentene, respectively. The mechanism of the first of these was investigated by kinetics and ('2)H labelling studies while a novel carboxylate bridged rhodium dimer was obtained in the latter. Possible mechanisms for these rearrangements are presented which may involve metallacycle intermediates.



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