Bates, George Benjamin (1995) Tetrahedrally coordinating ligands. Doctoral thesis, Durham University.
Selective ligand coordination of zinc over other metals such as copper (II) and iron (III) is desirable and has potential commercial uses in hydrometallurgy. With this in mind ligands have been synthesised that impart a tetrahedral donor array. Binding to zinc which prefers a tetrahedral binding geometry may achieve selectivity over other non-tetrahedrally coordinating metals. Di-N-alkylated bisbenzimidazole-4,4'-dicarboxylic acids have been synthesised and shown by proton NMR, ESMS and IR analysis to bind zinc as an [L(_2)Zn(_2)] species with selectivity over copper, nickel, lead and cadmium. Hence a reversal of the Irving- Williams sequence is observed. Aqueous extraction tests using a lipophilic N-alkylated derivative indicated that the observed selectivity over copper and iron (III) was not reproduced under these experimental conditions. The ligand began to extract in the pH 2.3-3.8 region.2,9-Diphosphinoxymethyl phenanthroline derivatives were synthesised and shown to bind nickel, copper and zinc with similar stability constants, with only marginal enhancement over that of the parent phenanthroline. The 1:1 complexes were produced at acidities below pH 2. Increasing the length of the pendent arm donor groups by using phenylacetic acid moieties did not enhance zinc selectivity. The donor group was not ideal and [ML(_2)] species were generated (i.e. an N(_4) donor set)Two phenol substituted 12N(_3) ligands were synthesised (N-linked and β-C- linked). Complex stability order followed die Irving-Williams sequence Cu > Zn > Ni. The N-linked derivative formed a six membered chelate on binding and had larger metal-ligand stability constants than for the C-linked derivative which formed an eight membered chelate. The N-linked derivative bound the copper (II) cation in a near tetrahedral arrangement and imparted some copper (I) character to the metal
|Item Type:||Thesis (Doctoral)|
|Award:||Doctor of Philosophy|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||09 Oct 2012 11:47|