Carbon-13, nitrogen-15, and phosphorus-31 NMR study of the scrambling and the redox reactions of some gold(I) complexes
[Thesis]
M. N. Akhtar
King Fahd University of Petroleum and Minerals (Saudi Arabia)
1996
205
Ph.D.
King Fahd University of Petroleum and Minerals (Saudi Arabia)
1996
The interaction of antiarthritic drug aurothiomalate (Autm)n with thiourea, selenourea, imidazoildine-2-selone, SCN and SeCN in aqueous solution has been studied using C NMR spectroscopy. It has been observed that the thiourea forms a 1:1 complex with (Autm)n, SCN causes an increase in the polymerization of (Autm)n, while, selenourea, imidazolidine-2-selone and SeCN cause redox reactions with (Autm)n to form metallic gold, metallic selenium and thiomalic disulfide. The characterization of polymeric gold(I)captopril (Aucap)n has been carried out using viscosity and electronic, mass, C and N NMR spectroscopies. It was observed that the degree of polymerization in (Aucap)n is much higher than that of (Autm)n. Mass spectroscopy has shown two characteristic routes of fragmentation. It has been observed that (Aucap)n also forms 1:1 complex with thiourea, while it undergoes a redox reaction with selenourea and SeCN to produce metallic gold, metallic selenium and captopril disulfide. The ligand scrambling reaction of R3PAuCN complexes to form ((R3P)2Au) and (Au(CN)2) species has been studied using C N and P NMR spectroscopy in a series of complexes. We have reported J(P-C), J(C-N), 2J(P-C) and J(P-N) coupling constants in these complexes and have observed various trends in them with respect to basicity of phosphine ligands. The free energy of activation in these complexes is also measured using P NMR band shape analysis. The antisymbiotic trans effect in a series of R3PAuSCN complexes has been studied using infrared, C, N and P NMR spectroscopies. It has been observed that unlike R3PAuCN complexes, the R3PAuSCN complexes do not undergo ligand scrambling reactions.