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.

Thesis (M.S. in Joint Campaign Planning and Strategy)--Joint Forces Staff College, Joint Advanced Warfighting School, 2007. / Title from title screen; viewed on July 9, 2007. "April 2007." Electronic version of original print document. Includes bibliographical references (p. 64-67).

The reaction of K[N{P(S)Ph2}2] (R = Ph or iPr) with [Mo(N3S2)Cl3] in dichloromethane gives [Mo(N3S2){(ph2(O)PNP(S)P2}2] 1 and [Mo(N3S2){iPr2(O)PNP(S)iPr2}2] 2. X-ray crystallography revealed in both compounds the chelates are co-ordinated to octahedral metal centres. The oxygen atoms are located in the trans position to the nitrogen of the triazene ring. The absence of a chloride counter ion indicates that the metal centre has been reduced from Mo(VI) to Mo(V), and electron paramagnetic resonance spectroscopy confIrmed the reduction of the molybdenum centres. The friction reducing study of compound 1 and [Mo(N3S2)(DTBC)2]Na (DTBC = 3,5–di–tert–butylcatechol) has shown that both compounds exhibit low friction coefficient values.

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

Le management des connaissances est présenté aujourd’hui comme un enjeu majeur du fonctionnement des organisations. Il permettrait un développement des capacités d’innovation de la firme et participerait au développement de son avantage concurrentiel. Bien que la thématique du management des connaissances ait été fortement explorée ces dernières années, certaines questions restent ouvertes. L’une d’entre elles porte sur la relation entre la création de connaissances et le principe d’organisation (« organizing »). En effet, une très grande majorité des approches actuelles en Knowledge Management s’intéresse principalement aux systèmes de gestion des connaissances et aux communautés de pratique mais ne questionne pas l’impact des principes fondamentaux de l’organisation sur les processus de création, de partage, de mémorisation de la connaissance. Notre travail se situe donc au croisement de deux champs de recherches : la coordination intra-organisationnelle et la connaissance organisationnelle. Suite à une exploration hybride, nous avons formulé notre problématique comme suit : « Comment les membres d’une équipe-projet parviennent-ils à se coordonner et construire de nouvelles connaissances ? ». Trois questionnements sous-jacents apparaissent dans cette problématique : le premier porte sur les pratiques de création de connaissances, le second aborde les pratiques de coordination, et enfin la meilleure compréhension des pratiques de coordination et des pratiques de création de connaissances permet de poser la question de leur relation. Après avoir mené une revue de littérature multidisciplinaire sur la connaissance dans l’organisation afin de rendre compte de la variété des approches, nous présentons dans notre second chapitre de la littérature sur la coordination intra-organisationnelle. Après avoir identifié les défis méthodologiques liés à l’étude de la connaissance dans l’organisation, nous présentons notre méthodologie basée sur les principes de l’étude de cas et les conseils de la théorie de l’acteur-réseau. Nos deux derniers chapitres présentent les données empiriques et les résultats de notre recherche. / Although knowledge management and organizational learning have been on the agenda for several years, some important questions remain unanswered. One of these questions is related to the link between organizing and learning. This thesis aims at understanding the links between practices of knowing and practices of “coordinating” in project teams. We especially study how collective coordination is crafted to deal with the impact of knowing and how the coordinated solutions arising from this coordination practice influence the next knowing practices. With the help of the Actor Network Theory (ANT), a longitudinal and qualitative study, five project teams explore the relation between learning activities and “networking” activities. Based on the findings of these five case studies, our conclusion points towards a view of coordination as a dynamic, socio-material, heterogeneous practices characterized by ongoing learning, transformations, and reconfigurations during “controversies”. Moreover, evidence is provided that the coordination mechanisms impacts the capacity of actors to create and share knowledge.

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.

Energy transfer between Reineckate ion (donor) and hexacyanochromate(III) ion (acceptor) has been studied through quenching of donor phosphorescence (lifetime and intensity) and sensitization of acceptor phosphorescence. Results from all measurements fit the expected Stern-Volmer relationship with a quenching constant kQH = 7.2 x 10⁵ M⁻¹ sec⁻¹ at -65°C. The pre-exponential factor and activation energy of kQH are 6.6 x 10¹º M⁻¹ sec⁻¹ and 4.8 Kcal/mol respectively. The constant, kQH’ is attributed entirely to an energy transfer rather than a quenching process. The electronic states directly involved are the ²Eg (and/or² T₁g) states of both donor and acceptor. Energy transfer is a diffusion-controlled (collisional) process. Hexacyanochromate(III) ion is itself quenched in the presence of Reineckate ion. The quenching constant, k'QH, which may be attributed to back energy transfer from acceptor to donor, has a pre-exponential factor of 2 x 10¹² M⁻¹ sec⁻¹ and an activation energy of 7.6 Kcal/mol. In the same system, quenching of photoaquation has also been studied at -65°C. The photoaquation quantum yield of Reineckate ion is 1.02 x 10⁻². It is reduced in the presence of hexacyanochromate(III) ion, but not as much as the phosphorescence of Reineckate ion is reduced. The limiting unquenchable part, ϕ∞chem, occurs via the ⁴T₂g state, while the quenchable part must occur through the ²Eg state as an intermediate. The actual path for the quenchable part proposed is back intersystem crossing from the ²Eg to the ⁴T₂g state, which then undergoes aquation. The primary processes of ²Eg state molecules have been investigated through the temperature dependence of phosphorescence lifetimes of some Cr(III) complexes. All the available evidence supports the idea of the thermally activated back intersystem crossing. According to this mechanism, the origins of the ⁴T₂g states of Cr (III)complexes reached by crossing are far lower in energy than has been expected. Assuming the occurrence of back intersystem crossing, the application of energy transfer to the determination of intersystem crossing quantum yield, ϕisc’ has been demonstrated. The values of ϕisc for Reineckate and hexacyanochromate (III) ions are estimated to be 0.52 and 0.35, respectively. The variation of ϕisc with temperature for these Cr(III) complexes has also been measured, which suggests that in general, internal conversion has a strong temperature dependence. From the rise of phosphorescence with time after pulse excitation, a new parameter, Tx, has been obtained which represents population of the phosphorescing state and is believed to be the lifetime of the ⁴T₂g (or less likely ²T₁g) state. Efforts have been made to confirm and identify this parameter. Studies of ϒx have been carried out as a function of temperature. Mechanisms based on different tentative assignments of ϒx are proposed and their implications examined. All primary processes, except the intrinsic radiative transitions, seem to consist of at least two components, which take different pathways and are different functions of temperature. / Science, Faculty of / Chemistry, Department of / Graduate