Date of Award


Degree Type


Degree Name

Doctor of Philosophy


This thesis describes the oxidative addition of alcohols, water and organic halides to dimethyl(2,2-bipyridine)platinum(II) (complex (I)) and to dimethyl(1,10-phenanthroline)platinum(II) (complex (II)). The work has involved characterising the reaction products and investigating the mechanism of oxidative addition. Up to now very little mechanistic work has been done for oxidative addition at platinum(II) centres.;Complexes (I) and (II) react with methanol, ethanol and isopropanol to produce the first series of platinum(IV) alkoxides of general formula {lcub}PtMe(,2)(OR)(N N)H(,2)O{rcub}('+){lcub}OH{rcub}('-) (N N = bipy or phen; R = Me, Et, ('i)Pr). Characterisation was achieved by ('1)H nmr, ('13)C nmr and elemental analysis. In an analogous reaction with water the product was a platinum(IV) hydroxo complex.;Primary organic halides reacted cleanly with complex (II) to produce complexes of general formula {lcub}PtXMe(,2)(R)(phen){rcub} (X = I or Br; R = Me, Et, ('n)Pr, ('n)Bu). The reactions proceed via an S(,N)2 mechanism.;The reaction of complex (II) with methylene dihalides is believed to proceed via the intermediacy of free-radicals. The reaction of CH(,2)X(,2) (X = Cl, Br or I) with (II) produced a mixture of cis- and trans-isomers of general formula {lcub}PtXMe(,2)(CH(,2)X)(phen){rcub}. Complex (II) reacted with CH(,2)ClI producing a mixture of platinum(IV) complexes, which involved halogen scrambling.;The reaction of X(CH(,2))(,2)X (X = I or Br) with (II) is thought to proceed via competing radical chain and radical non-chain mechanisms. The novel binuclear complexes {lcub}Pt(,2)X(,2)Me(,4){lcub}(CH(,2))(,2){rcub}(phen)(,2){rcub} were isolated from these reactions.;The reaction of (II) with an excess of the (alpha),(omega)-diiodoalkanes I(CH(,2))(,n)I (n = 3-5) produced mononuclear complexes of general formula {lcub}PtIMe(,2){lcub}(CH(,2))(,n)I{rcub}(phen){rcub}. The reaction proceeds via an S(,N)2 mechanism. These mononuclear complexes reacted further with (II), also via an S(,N)2 mechanism to produce the binuclear bridging polymethylene complexes, {lcub}Pt(,2)I(,2)Me(,4){lcub}(CH(,2))(,n){rcub}(phen){rcub}. The rate-constants for these reactions could be measured and indicate a neighbouring atom effect for the reaction of the complexes, {lcub}PtIMe(,2){lcub}(CH(,2))(,n)I{rcub}(phen){rcub}, with (II). In deoxygenated solvent isopropyl iodide reacted with (II) to form {lcub}PtIMe(,2)(('i)Pr)(phen){rcub}. However, in the presence of dioxygen the major product was {lcub}PtIMe(,2)(('i)PROO)(phen){rcub}. This is the first platinum(IV)peroxo complex to be isolated and a single crystal x-ray structure was performed for this complex. . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of author.) UMI



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