A spectroscopic study of square planar platinum (2) complexes
Master Thesis
1983
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University of Cape Town
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Abstract
A number of spectroscopic techniques consisting of ultraviolet, ¹H-NMR and mass spectrometry have been used in the structural analysis of square planar Pt(II) complexes. The complexes trans-[PtBr₂(Y) (R-an)] (Y = C₂H₄,CO; R-an = substituted aniline) were prepared and investigated by the spectrosopic techniques. Infrared assignments were aided by isotopic labelling studies. The discussion of the two series of complexes are based on their relation to one another. The complexes trans-[PtX₂ (CO) (L)] (X = Cl, Br; L = aniline, pyridine N-oxide, pyridine, ammonia, imidazole and pyrazole) were prepared from their corresponding ethylene analogues. Infrared assignments, with labelling studies, are given for the complexes. The bonding effects in these complexes were studied using ¹H-NMR and ultraviolet spectroscopy. The ¹H-NMR spectra reveal that there is a fluxional behaviour of the ligands in some of the complexes. Hence, cold temperature studies were required to "freeze out" this fluxional behaviour and observe the expected signals due to the ¹⁹⁵pt-H coupling. The electronic effects are different when the ligand, L, was capable of forming σ-bonds with Pt²+, compared to when L was capable of forming both a- and π-bonds with Pt²+. The mass spectra show the M+ peak and subsequent fragmentation in the complexes. The fluxional behaviour of imidazole in trans-[PtX₂(C₂H₄) (Him)] was monitored by cold temperature studies. Using band shape analysis (with the aid of a computer) the activation paramaters for the exchange processes were determined. The dependence of the imidazole proton signals on temperature, solvent and excess ligand, all indicate that an intermolecular exchange process is occurring. Studies on the complex trans-[PtX₂(C₂H₄) (pyz)] and the effect of solvent on the complexes are being pursued, and it is hoped that an understanding of the role of the solvent in the exchange process will become apparent.
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Bibliography: pages 143-148.
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Reference:
Hall, P. 1983. A spectroscopic study of square planar platinum (2) complexes. University of Cape Town.