We use cookies to ensure that we give you the best experience on our website. By continuing to browse this repository, you give consent for essential cookies to be used. You can read more about our Privacy and Cookie Policy.

Durham e-Theses
You are in:

Chemistry of functionalised macrocycles

Matthes, Karen Elizabeth (1987) Chemistry of functionalised macrocycles. Doctoral thesis, Durham University.



The work reported in this thesis is divided into two distinct areas. The first involves the synthesis of monoaza- and diaza-[12]-ring macrocycles, with differing side-arm N-substituents. The twelve-membered macrocycles possess a convenient ring-size for exploring the stability and selectivity of complexation of small cations, in particular those from groups IA and IIA. Amide substituents on nitrogen were expected to function as effective σ-donors to cations with high charge density (e.g. Li (^+), Ca (^2)(^+)), because of their high ground state dipole moments. The effect of the length of the side-arms attached to nitrogen on the complexation has also been studied. Complexation behaviour has been probed using (^13)C NMR spectroscopy, titration calorimetry, and fast-atom bombardment mass spectroscopy. Copper (II) complexes of three of the [12]-ring cycles have also been characterised by X-ray crystallographic analysis. The second area involves the study of a series of macrocyclic ligands capable of forming homo- and hetero-dinuclear complexes. In particular, ligands containing the pyridyl-dithio (PyS(_2)) binding unit and a polyether chain linking the two sulphur atoms have been examined. The three binding atoms of each PyS (_2) group define three corners of a fairly rigid square planar environment which favours the formation of square planar d(^8) complexes. Accordingly, complexation with rhodium (I) [and (III)], palladium (II), and platinum (II) has been investigated: the structural properties of these complexes have been determined by the use of FT NMR and X-ray crystallography.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1987
Copyright:Copyright of this thesis is held by the author
Deposited On:08 Feb 2013 13:45

Social bookmarking: del.icio.usConnoteaBibSonomyCiteULikeFacebookTwitter