Thesis (M.Sc. (Environmental Science and Management)--North-West University, Potchefstroom Campus, 2008

Thesis (M.Sc. (Environmental Science and Management)--North-West University, Potchefstroom Campus, 2008

Thesis (M.Sc. (Environmental Science and Management)--North-West University, Potchefstroom Campus, 2008

Orientador : Antonio Luiz Pires Valente / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-19T03:05:56Z (GMT). No. of bitstreams: 1 Rocha_EduardoCarasekda_M.pdf: 5109549 bytes, checksum: 78572e4290a3ae50d886e555bec8167e (MD5) Previous issue date: 1994 / Mestrado

<p> Reaction of the hydrated trichlorides of rhodium and Iridium with hexamethyldewarbenzene gave the complexes, (C5Me5MCl2)2 (M=Rh, Ir). A mechanism for this reaction is proposed.</p> <p> The dichloro complexes, (C5Me5MCl2)2, were reacted with a number of di- and tri-enes in ethanol in the presence of base and gave a variety of pentamethylcyclopentadienyl complexes of M(l) and M(lll). Evidence for a hydrido intermediate is presented and the hydrido- and deuterido- complexes, C5Me5IrH(D)ClPPh3, were isolated and characterised.</p> <p> The isomers endo-H and exo-H pentamethylcyclopentadiene(cyclopentadienyl) rhodium were isolated and showed significant differences in their properties. Cyclooctadienes reacted with (C5Me5MCl2)2 to give C5Me5M(1,5-C8H12) via the intermediacy of the π-2-cyclooctenyl complexes C5Me5MCl(C8H13); mechanisms are presented to account for the observed products. Cyclohexadienes gave the complexes, C5Me5M(1,3-C6H8). 1,4-Cyclohexadiene was isomerised to 1,3-C6H8; the rhodium complex, C5Me5Rh(1,3-C6H8), was a very active catalyst for the disproportionation of 1,3-C6H8 to cyclohexene and benzene, both ethanol and base were cocatalysts.</p> <p> Mass spectral data for these and other organo-metallic complexes are presented.</p> / Thesis / Doctor of Philosophy (PhD)

Comme le naphtalène a récemment émergé comme un socle fondamental en chimie médicinale, le développement de méthodologies menant à des plateformes fonctionnalisées basées sur du naphtalène est devenu un centre d’intérêt majeur de la communauté scientifique. En effet, des conditions expérimentales optimisées sur le benzène ou d’autre noyaux aromatiques ne peuvent pas toujours être transposées au naphtalène. Ces dernières peuvent parfois conduire à des résultats différents, possiblement dû à l’aromaticité plus faible de ce bicycle aromatique.Dans ce contexte, cette thèse s’articule autour du naphtalène et de ses dérivés. Des méthodes variées permettant une fonctionnalisation sélective de différentes positions de cette plateforme, ainsi que des stratégies de synthèses d’architectures polycycliques ont été développées.Notre attention s’est ensuite portée sur des précurseurs du naphtalène, en particulier sur les tetralones. En utilisant une méthode basée sur l’utilisation d’un groupe directeur éphémère, la position 8 de ce bicycle a été arylée, et les différents composés ainsi obtenus ont pu être convertis en d’autre plateformes polycycliques. En complément, des calculs DFT ont permis d’expliquer la régiosélectivité observée lors de la synthèse de fluorenones étendues, et d’étudier le mécanisme d’arylation dirigée des tetralones. / Because naphthalene has recently emerged as a fundamental platform in medicinal chemistry, the development of methodologies leading to diversely functionalised naphthalene-based platforms has become a prime concern of the scientific community. Indeed, experimental conditions previously optimised for benzene and other aromatic rings cannot always be applied to naphthalene. These methods can sometimes lead to different results, as a consequence of the lower aromaticity of the naphthalene core.In this context, this thesis is dedicated to the naphthalene and its derivatives. Various methods to selectively functionalise the different positions of the naphthalene core and synthetic pathways to extended polycyclic architectures were developed.Next, we focused on naphthalene precursors, especially on tetralones. Using a strategy involving a transient directing group, the position 8 of these bicycles was successfully arylated and the resulting compounds were successfully converted into other polycyclic platforms. In addition, DFT calculation have been used to explain the regioselectivity observed during the synthesis of extended fluorenones, and to study the mechanism of directed arylation of tetralones.

Chapter 1 introduces the discovery of elemental fluorine by H. Moissan and some uses of inorganic fluoride. Organo fluoro compounds and their place in pharmaceuticals and agrochemicals are also introduced. The general properties of fluorine and the C-F bond are discussed as well as conformational influences such as the fluorine gauche effect. Chapter 2 describes the C-N⁺------F-C charge dipole interactions within protonated amines and explains the influence of a β fluorine on the conformation on various crystalline structures. A number of systems are synthesised which contain this charge dipole interaction, such as four, five and eight membered aza heterocycles. It was demonstrated that these provided a N⁺-C-C-F gauche torsion angle. This electrostatic effect was also observed in the non-protonated N-ethylpyridinium cations possessing a fluorine β to the charged nitrogen. This clearly showed that hydrogen bonding is not playing a part in the observed N⁺-C-C-F gauche interactions and that it is a purely electrostatic effect. Chapter 3 discusses the effort to explore the C-O⁺-------F-C charge dipole interaction and the synthetic approaches that were taken towards candidate substances. However in the event a Grignard reaction on a fluoro cyclohexanone was found to provide an unexpected product where rearrangement followed by fluorine elimination had occurred. Chapter 4 details the experimental procedures for the compounds synthesised in this thesis and an Appendix outlines the detail of 24 crystal structures that were solved during this research.

Three studies were completed to investigate the influence of mineral assemblage on soil organic carbon (SOC) cycling and pedogenesis in forest soils. Two studies utilized a lithosequence of four parent materials (rhyolite, granite, basalt, limestone/volcanic cinders) under Pinus ponderosa, to explicitly quantify the contribution of parent material mineral assemblage to the character of the resulting soil. The first study explored variation in pedogenesis and elemental mass loss as a product of parent material through a combination of quantitative X-ray diffraction and elemental mass balance. Results indicated significant differences in degree of soil development, profile characteristics, and mass flux according to parent material.The second study utilized the same lithosequence of soils, but focused on organic C cycling. This study explored variation in SOC content among soils of differing mineralogy and correlations among soil physiochemical variables, SOC content, soil microbial community composition and respiration rates. Metal-humus complex and Fe-oxyhydroxide content emerged as important predictors of SOC dynamics across all parent materials, showing significant correlation with both SOC content and bacterial community composition. Results indicated that within a specific ecosystem, SOC dynamics and microbial community vary predictably with soil physicochemical variables directly related to mineralogical differences among soil parent materials.The third study focused specifically on the influence of goethite and gibbsite on dissolved organic matter characteristics and microbial communities which utilize DOM as a growth substrate. Iron and aluminum oxides were selected for this study due to their wide spread occurrence in soils and their abundance of reactive surface area, qualities which enable them to have a significant effect on SOC transported through forest soils. Results indicated that exposure to goethite and gibbsite surfaces induces significant differences in DOM quality, including changes in thermal properties, molecular structure, and concentrations of P and N. Investigation of the decomposer communities indicated that exposure to goethite and gibbsite surfaces caused significant differences in microbial community structure.These investigations emphasize the important role of mineral assemblage in shaping soil characteristics and regulating the cycling of C in soils, from the molecular scale to the pedon scale.

Coagulation is a ubiquitous process in the treatment of raw surface water for eventual potable use. Despite its capabilities, the sheer scale of its use is manifested in the volumes of chemicals it demands and waste sludge it produces. Recovering and reusing the chemical activity of the coagulant sludge in water treatment is a logical solution but this practice has been restricted by the presence of contaminants within the sludge. This thesis has investigated methods that can separate the coagulant metals from these primarily natural organic contaminants, with an aim of producing a sufficiently pure coagulant for effective treatment performance when reused. A process of ultrafiltration of the impure regenerated coagulant followed by a powdered activated carbon polishing stage compared favourably to a number of other separation processes and was found to remove the most dissolved organic compounds. When the purified coagulant was used to treat raw water, it provided better turbidity removal than commercial coagulant and matched its removal of trihalomethane precursors, making the process suitable for consideration at full-scale. Analysis of the whole life cost suggested that such performance could be reproduced at full-scale within a 25 year payback period. The reuse of even purified recovered coagulants in drinking water treatment still carries risks which may deter its implementation. Therefore the efficacy of recovered coagulants in the role of phosphorus removal from wastewater was also investigated. This showed that both acidified and unacidified waterworks sludges, with sufficient contact time, could remove similar levels of phosphorus as fresh coagulants, at approximately half the whole life cost.

The prevalence of fluorine in natural products is scarce. There are but a handful of compounds that have been discovered to date. This could be largely attributable to the occurrence of fluorine in nature as fluoride (F-). — One might recognize such nomenclature from the ingredients list on a toothpaste tube — In fact, naturally occurring fluoride is most commonly found as fluorite (CaF2) or cryolite (Na3AlF6). As such, the introduction of fluorine via biological pathways has been limited to use of aqueous F- (a very poor nucleophile). This fact — coupled with its naturally low concentration in water — has created the ripe conditions for this shortage. In a way this has proven fertile for synthetic chemists because nature has not yet evolved a method for the deconstruction of partially or fully fluorinated compounds. Considering the above, as synthetic methodologies for the construction of carbon-fluorine bonds became available, so too did the discovery of their valuable properties. So beneficial are these properties that C-F bond-containing compounds have become commonplace in many households throughout the world. For example, practically every home relies on these compounds for use in their refrigerators. Other examples of useful fluorinated materials include blowing agents, non-stick coatings, pharmaceuticals, agrochemicals, liquid crystals, and lubricants. With all these applications and seemingly easy availability of these compounds, it is interesting to learn that original synthetic methods are still being employed today. As such, the objective of this Thesis is to develop ‘greener’ routes for the synthesis of fluorocarbons. We hypothesized that by studying transition metal-fluoroalkyl complex-mediated reactions, a more efficient catalytic system could be developed. A foreseen complication arises from the thermodynamic stability of C-F, transition metal-F and transition metal-CRF bonds. Improvements to overcome these caveats include the use of first-row late transition metal complexes. Presented herein are additions to this body of knowledge by expanding on the reactivity of nickel, copper and silver fluoroalkyl complexes. The approach applied in this work, in line with ‘green’ chemistry principles, was to source readily available fluorinated reagents, i.e. fluoroalkenes and fluoroarenes, to reduce the number of steps for the synthesis of new fluorinated compounds. Chapter 2 builds on the well-established oxidative cyclization of C2 fluoroalkenes to nickel (0), which yields new C4 units. The use of a bulky N-heterocyclic carbene ligand was found to enhance reactivity by reducing the coordination number at nickel. Examples of room temperature Cα-F and Ni-CF bond activation and functionalization reactions are presented. Chapters 3, 4 and 5 re-examine the insertion of fluoroalkenes into silver and copper fluorides and hydrides. Building on precedent of addition reactions to hexafluoropropene, this fluoroalkene was examined first. In so doing, a versatile and inexpensive copper heptafluoroisopropyl reagent was developed (Cu-F addition to (CF3)CF=CF2. With easy access to new heptafluoroisopropyl complexes, they were systemically studied for their applications in catalysis. This revealed key features, particularly the lability of the M-hfip bond, which could be detrimental to catalytic reactions. As such, a nickel complex-mediated carbonylative heptafluoroisopropylation reaction and copper complex-mediated nucleophilic addition to electrophiles were developed. When a copper hydride was used instead, the in situ generated fluoroalkyl [Cu-H addition to (CF3)CF=CF2] was susceptible to β-fluoride elimination. Chapter 4 expands this methodology to achieve the catalytic consecutive hydrodefluorination of fluoroalkenes, demonstrating the scope and limitations of this system. Furthermore, the critical role of the phosphine ligand in accessing an L3Cu-H addition and unusual β-fluoride elimination mechanism is highlighted. However, tetrafluoroethylene proved resistant to this reaction because the fluoroalkyl resting state of this alkene, Cu-CF2CF2H, is unusually robust. Chapter 5 investigates the utility of this fragment and others in C(sp2)-RF cross-coupling and nucleophilic substitutions. With focus on new routes for late stage fluorination and examples of nickel (0) complex-catalyzed selective C-F bond functionalization reactions, Chapter 5, continues studies for low-temperature and DMAP-assisted conditions for aryl-F cross-coupling reactions with boronic acid esters. Lastly, Chapter 6 reviews the advances presented in this Thesis, provides a link to the expected lasting impacts and attempts to provide guidance to future research on transition-metal complexes in the synthesis of C-F or C-RF containing compounds. Moreover, with the introduction of a new hydrodefluorination technology, previously scarce fluoroalkenes (e.g. 1,2-difluoroethylene) can now be used more freely, potentially leading to the development of new refrigerants or materials applications.