SYNTHESIS OF NITROGEN/SULFUR LIGANDS AND THEIR METAL COMPLEXES

The first part of this thesis is concerned with the preparation of small molecule models for the active site in copper "blue" enzymes. The models proposed are copper complexes of a series of "tripod" ligands containing nitrogen and sulfur donor atoms.; The ligands investigated are 5-(bis(2-mercaptoethyl)amine)methyl-2-ethyl-4-methylimidazole (L), 5(4-(1,7-dithia-4-azaheptane)methyl)-2-ethyl-4-methylimidazole (V) and N-(2-benzimidazolylmethyl)-N,N-bis(2-ethylthioethyl)amine (BIET).; The ligands L and BIET have the potential to act as tetradentates. Metal complexes of L are complicated polymeric species making them difficult to study. Metal complexes of BIET are probably trigonal bipyramidal. The binding of BIET to the diamagnetic metal Cd(II) was studied using H-1 and C-13 NMR spectroscopy.; The ligand V has the potential to bind as a bidentate or tridentate. C-13 NMR studies of the Cd(II) binding to V suggest a 1:1 metal:ligand complex forms. X-ray structural analysis of Cd(II)VBr(,2) shows that the ligand acts as a bidentate. The aliphatic amine and imidazole nitrogen of V coordinate to Cd(II).; The remainder of this thesis is concerned with the coordination chemistry of ligands containing amines and sulfoxides. The ligands investigated include the bidentate methylsulfinylpropanamine (MSPA); the tridentates di(aminoethyl)sulfoxide (daso) and bis(alkylsulfinylethyl)amine (asea); and the tetradentate N-(2-benzimidazoylemthyl)-N,N-bis(2-ethylsulfinylethyl)amine (BIEOT).; Sulfoxides are ambidendate ligands. The metal can bind to either the oxygen or sulfur. The different modes of binding can be distinguished using IR or NMR spectroscopy. Spectral studies of the Pt(II) complexes of MSPA, dase and asea suggest that the Pt binds to the sulfur. This was confirmed by x-ray structural studies of Pt(II)(MSPA)Cl(,2). Spectral studies of the Cd(II)BIEOT complex suggests that the Cd binds to the oxygen.