Typescript. / Thesis (Ph. D.)--University of Hawaii, 1968. / Bibliography: leaves [83]-85. / viii, 85 l graphs, tables

Thesis (Ph. D.)--University of Oregon, 2007. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 307-324). Also available for download via the World Wide Web; free to University of Oregon users.

Thesis (Ph. D.)--University of Washington. / Bibliography: L. [85]-88.

Thesis (Ph.D.)--Drexel University, 2009. / Includes abstract and vita. Includes bibliographical references (leaves 201).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1941. / Typescript. Includes abstract and vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 90-92).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1971. / Vita. Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2003. / Supervisor: Alan H. Cowley. Vita. Includes bibliographical references. Also available from UMI.

Irradiation of [special characters omitted] at 313 nm in basic solution at 10°C in the presence of free SCN yields the products [special characters omitted], and [special characters omitted]. Analysis of product distribution was done by HPLC using a [special characters omitted] column and ion pairing reagents with methanol and water as the eluent. The aquation/anation product ratio is independent of X, but depends linearly on the concentration of SCN. A specific ion effect is observed, the aquation/anation ratio showing a correlation with the radius of the cation. The ratio of sulfur to nitrogen thiocyanato product is 10±2, independent of X, concentration of SCN, and cation, but is different that measured in the thermal anation of [special characters omitted] which gives a S/N ratio of 4. A limiting dissociative mechanism is proposed for the photosubstitution, involving a five coordinate intermediate of sufficient kinetic stability to discriminate among entering groups. The constant S/N ratio for the photosubstitution leads to the conclusion that the intermediate formed in the photoreaction is different from that formed in the thermal reaction. Direct anation has been reported previously for aquopentacyanocobaltate, but not for hexacyanocobaltate. Quenching of the emission lifetime of [special characters omitted] in the presence of chloride salts shows the same order of cation assistance with cation radius as observed for the aquation/anation ratio. / Graduate

A range of novel ligand systems have been developed in three distinct phases and preliminary studies have been initiated to evaluate their complexation potential. Phase I incorporated the synthesis of single strand ligand systems, which were mainly based on amino acid residues. Techniques have been developed for the attachment of these ligand systems onto, firstly, a styrene monomer, and then later onto a pseudo-styrene linking group, viz. the p-toluoyl group. The linking reactions were based on the formation of amides or esters by the reaction of an acid chloride system with an amine or alcohol. Phase II involved the synthesis of bis-chain ligand systems and their attachment onto the p-toluoyl linking group. A further linking group was also developed at this stage, viz. the xylyl group. In the preparation of phase II ligand systems, use was made of malonic ester and iminodiacetic acid derivatives. Phase III has involved the synthesis of cyclic ligand systems, with skeletons based upon the structures used in phase I and phase II and two crown ether type systems have been prepared.

The application of bidentate N,N'-donor ligands, such as 2,2'-biimidazole (BIIMH2) and 2,2'-pyridylimidazole (PIMH) and (1H-benzimidazol-2yl)-N-methylmethanamine (BIMAH), in the solvent extraction of base metal ions from an acidic sulfate/sulfonate medium was investigated. PIMH and BIMAH showed selectivity for Ni(II) with the only interfering ion being Cu(II) in the pH range 1.2-1.8 but BIIMH2 lacked selectivity. The extraction patterns observed were influenced by stereochemical aspects, and this agreed well with the envisaged design of nickel(II)-specific extractants through stereochemical “tailor-making” which is proposed in this study. The extraction patterns were explained from a coordination chemistry point of view using spectroscopic analysis and single crystal X-ray analysis to diagnose the geometry of the complexes formed from the interaction of the base metal ions with the ligands. The formation of the trigonal bipyrimidal [Cu(PIM)2(H2O)](SO4) complex, with a water molecule coordinated, while nickel(II) forms a square planar bisPIMH was put forward as the reason for extraction pattern observed with this ligand. Cobalt(II) also forms a bisPIMH complex but has two water molecules coordinated in the formation of a distorted octahedral complex, and this results in less extractable species. A similar observation as for PIMH was noticed in BIMAH complexation reactions. The BIIMH2 complexes were found to be distorted octahedral, through the bis-coordination of BIIMH2 and two sulfonate ions, resulting in lack of pH-metric separation of the later 3d metal ions. The stability constants data was in agreement with what was observed in the solvent extraction and coordination chemistry studies for the three ligand systems.