This project was aimed at synthesising, characterising and examining the properties of the novel polyamine ligand 4’-{2’”-(12-Amino-2,6,9-triazadodecyl)-phenyl}-2,2’:6’,2”-terpyridine and its related complexes. The ligand would be based around the 4’-(o-toluyl)-2,2’:6’,2”-terpyridine framework and have potential applications in analytical chemistry. The 4’-(o-toluyl)-2,2’:6’,2”-terpyridine framework would have a tail attached on the functionalised o-toluyl methyl group. The ortho toluyl functionality was chosen so that the donor atom containing tail would be directed back towards the coordination site. This would make it easier for the tail to interact with a central metal ion. There is potential to be able to change the number and type of donor atom in the tail so that the ligand may be metal ion selective. As the tail would contain donor atoms, the denticity of the ligand would be increased making it more applicable for complexometric titrations. The 2,2’:6’,2” terpyridines exhibit strong colours when coordinated to selective metal ions and so would have potential applications in colorimetry also. The ligand was successfully synthesised and characterised. In a multi-step process, the 4’-(o-toluyl)-2,2’:6’,2”-terpyridine underwent radical bromination before the tail was attached. The tail used in this research was N,N'-bis (3-aminopropyl)ethane-1,2-diamine (3,2,3-tet). The secondary amines in this polyamine tail were protected before addition to the brominated 4’-(o-toluyl)-2,2’:6’,2”-terpyridine to ensure terminal addition. After the tail addition, a two step separation process purified a sample of 4’-{2’”-(12-Amino-2,6,9-triazadodecyl)-phenyl}-2,2’:6’,2”-terpyridine for analysis. Due to the late stage in this research where a successful separation technique was found, little work was done on examining the properties of this ligand and its complexes.

Complexes of the type MX(η²-NO₃)(CO)₂(PPh₃)₂, (M = Mo, X = Cl, Br; M = W, X = Br) were prepared from the reactions of MX₂(CO)₂(PPh₃)₂ with ammonium nitrate in acetone. The complexes were characterized by elemental analyses, ¹⁵N labelling, infrared and NMR spectroscopy. The nitrate ligand is bidentate and the complexes are seven-coordinate. Novel nitrite complexes of molybdenum and tungsten of the type M(NO₂)₂(PPh₃)₂ were prepared. The compounds were characterized by elemental analyses, ¹⁵N labelling, infrared and multinuclear NMR spectroscopy. Both NO₂ ligands are chelating and the two NO₂, PPh₃ and CO ligands are equivalent. Molybdenum dinitrosyl complexes were synthesized by the reduction of nitrate ions. The crystal structure of cis-dinitrosyl-cis-dichloro-trans-bis-(triphenylphosphine)molybdenum(II) was determined by x-ray diffraction. Both the nitrosyl groups are linear. Mo(NO)₂Cl₂(OPPh₃)₂ and Mo(NO)₂Cl(NO₃)(OPPh₃)₂ were synthesized by the reaction of MoCl(η²-NO₃)(CO)₂(PPh₃)₂ with NO in acetone/toluene mixture. The nitrosyl ligands are linear and the phosphineoxide ligands are cis to each other. The dinitrite complex Rh(NO)(NO₂)₂(PPh₃)₂ of the series Rh(NO)X₂(PPh₃)₂ (X - monodentate anions) was prepared as a direct derivative of Rh(NO)Cl₂(PPh₃)₂ by its reaction with sodium nitrite. The complex is square pyramidal with an apical nitrosyl ligand. The two NO₂ groups are present as the nitro and the nitrito group. Rh(NO)(NO₂)₂(PPh₃) reacted with oxygen and formed Rh(NO₃)₃(PPh₃)₂. The reaction of Rh(NO)(NO₂)₂(PPh₃)₂ with CO in acetonitrile produced Rh(CO)(NO₂)(PPh₃)₂. The complex Rh(CO)(NO₂)(PPh₃)₂ is square planar with the phosphine ligands in the trans positions.

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