Co-ordination and organometallic chemistry of facially capping tridentate macrocycle [12]-ane-P3(IPR)3

• Main Author: Pothupitiya, Thusith Kosala
• Published: Cardiff University 2010
• Subjects: 547
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.584959

The co-ordination chemistry of metal-phosphine complexes has developed dramatically since its appearance in 1857 by Hofman 11 and now it is one of the major areas in inorganic chemistry. The architecture of phosphine ligands to stabilise unusual complexes and oxidation states is the major contribution for the increasing interest in the chemistry of metal-phosphorous compounds. However, due to the difficulties in their synthesis, phosphorous-based macrocycle systems are rare in comparison to the other systems of analogous nitrogen-based macrocyles. This thesis concerns the detailed study of the chemistry of triphosphamacrocycle ligands with metals of iron, ruthenium, nickel and copper sub-groups. Specifically Fe(II), Ru(II), Ni(II), Ni(I), Ni(0) and Cu(I)X where X is CI, Br and I complexes of 1,5,9-triphosphacyclododecane ligands their syntheses, characterisation and structural analysis have been studied. In Chapter 1, the background of this project is explained. The radical-initiated template coupling of three facially co-ordinated allylphosphine ligands on a neutral (CO)3Mo(0) template leads to the co-ordinated tri-secondary macrocycle, 12-ane-P3H3. The synthesis of tertiary derivatives is two fold, one involving the deprotonation fallowed by alkylation at co-ordinated phosphorus by alkyl halide, in this study the use of Na-dimsyl as a deprotonating agent is documented. The macrocycle {12-ane-P3('Pr)3} is liberated by the oxidation of the template complex stereospecifically as the syn-syn isomer in high yield and its co-ordination chemistry with Fe(II) and Ru(II) is detailed in chapter 2. In Chapter 3, co-ordination studies of triphosphacyclododecane ligand with various oxidation states of nickel compounds has led to a range of novel macrocycle complexes, and they are characterised by multinuclear NMR and infrared spectroscopy. In Chapter 4, the preparation of novel Cu(I) complexes, which contain the macrocycle ligand is reported and described the very first X-Ray crystal structure of Cu(I) bimetallic species.