Master of Science
Dr. Richard J Puddephatt
This thesis describes a study of dimethylplatinum(II) complexes containing bidentate nitrogen donor ligands. This work deals with the oxidative addition of peroxides and focuses on synthesis, characterization and reaction mechanisms of these complexes.
Dimethylplatinum(II) complexes were reacted with oxidants dimethyldioxirane (DMDO), meta-chloroperbenzoic acid (m-CPBA) and phthaloyl peroxide. The use of these oxidants has allowed for the synthesis of novel platinum(IV) complexes by oxidative addition and the formation of unique supramolecular networks. The formation of both trans- and cis-oxidative addition products was controlled by the type of oxidant utilized. By varying the ligand design of the platinum(II) complexes, the formation of the multiple platinum(IV) complexes have been obtained, each demonstrating their own unique chemistry.
In other interests, low temperature 1H NMR spectroscopy has been utilized to follow the reaction pathway of the oxidative addition of iodine at [PtMe2(bpy)]. This technique allowed for the observation of intermediates formed within this reaction. The formation of intermediates shows solvent dependence following the trend; acetone >CD2Cl2 > toluene, suggesting there is stabilization of these intermediates by more polar solvents.
Pellarin, Kyle R., "Reactivity of Dimethylplatinum(II) Complexes with Peroxides" (2012). University of Western Ontario - Electronic Thesis and Dissertation Repository. Paper 705.