No description available.

The following thesis outlines work carried out during the last three years for the development and investigation of methodologies using amides as N- and O- acylating agents. Chapter 1 highlights the range of methodologies and protocols reported in the literature that use amides as precursors for the synthesis of both functionalised amides and esters. The introduction will highlight the range of catalysts and promoters used as well as the scope of the current methodologies. As well as this it will highlight the limitations of the methodologies so emphasising where the following research fits into these areas. Chapter 2 presents the development of a transamidation methodology using zirconocene dichloride as a catalyst. The scope with respect to functional group tolerance is presented as well as the investigations into the mechanism of the reaction. Chapter 3 builds on the research presented in Chapter 2 and details the development of a more catalytically active zirconocene transamidation methodology. By the addition of a catalytic additive the temperature or time required for the reaction to be carried out could be lowered. Investigations into the mechanism were also carried out highlighting the in situ formation of an active catalytic species. Chapter 4 details the development of an operationally simple methodology for the O-acylation of alcohols using amides. Using a catalytic amount scandium triflate the substrate scope of the reaction was explored with a proposed mechanism presented based on activation of the amide.

Chapter one introduces N-heterocyclic carbenes (NHCs) and discusses their use as ligands for rare earth metal complexes, with particular emphasis upon compounds synthesised from 2009 until the present day. Chapter two details the synthesis and characterisation of the homoleptic scandium-NHC complex [Sc(L)3] (L = [OCMe2CH2(1-C{NCHCHNiPr})]). Reactions of [Sc(L)3] with boranes, CO2 and CS2 are described which exploit the relative lability of the Sc–Ccarbene bond and allow formation of [Sc(L)2(OCMe2CH2(1-B'C{NCHCHNiPr}))] (B' = 9-BBN, BPh3, B(C6F5)3, BH3), [Sc(OCMe2CH2(1-O2CC{NCHCHNiPr})3]n, [Sc(L)2(OCMe2CH2 (1-S2CC{NCHCHNiPr})] and [Sc(L)(OCMe2CH2(1-S2CC{NCHCHNiPr})2]2. The chapter also discusses the reactivity of [Sc(L)3] towards substrates containing acidic C–H and N–H bonds and substrates containing polar E–X bonds (where E = C, Si, B, P and X = Cl, I). Chapter three describes the synthesis and characterisation of the NHC substituted scandium benzyl complexes [Sc(Bn)2(L)]2 and [Sc(Bn)(L)2], and the attempted synthesis of NHC substituted scandium aminobenzyl complexes. The reactivity of [Sc(Bn)2(L)]2 with RX substrates (R = alkyl) is discussed in detail; depending on the nature of the alkyl group, these reactions can allow formation of R–Bn , the result of carbon-carbon coupling. The complex [Sc(Bn)(L)Cl]2 has been isolated from these reactions and is structurally characterised. The reactivity of [Sc(Bn)2(L)]2 towards C–H bonds is explored and attempts to prepare NHC substituted scandium hydrides are described. Comparisons of the relative stability and reactivity of [Sc(Bn)2(L)]2 and [Sc(Bn)3(thf)3] are drawn. Chapter four documents the synthesis and characterisation of [Sc(Odtbp)2(L)] (Odtbp = 2,6-di-tert-butylphenoxide), [Sc(Odtbp)(L)2], and the samarium analogue [Sm(Odtbp)(L)2]. The reactivity of these complexes towards various small molecules is described. The chapter also details attempts to prepare the cationic scandium complexes [Sc(L)2][Bort] (Bort = bis[3,3',5,5'-tetra-(tert-butyl)-2,2-diphenolato]borate) and [Sc(L)2][B(Ph)4]. Chapter five provides overall conclusions to the work presented in this thesis. Chapter six contains all experimental and characterising data for the complexes and reactions detailed in this work.

This thesis reports the study of the molecular and electronic structure of scandium monohalides using the technique of laser ablation/reaction with supersonic free jet expansion used for producing the target molecules and laser induced fluorescence (LIF) spectroscopy for recording their electronic transition spectrum. The scandium diatomic molecules studied in this work were scandium monoiodide (ScI) and scandium monobromide (ScBr), which were produced by the reaction of Sc atoms with 2% CH3I and 2% C2H5Br gases seeded in Ar carrier gas, respectively. The LIF spectrum of the electronic transition of ScI and ScBr were recorded in the visible and near infrared spectral region between 613 and 854 nm. The analysis of the high resolution electronic spectra of ScI and ScBr yielded molecular constants and information of electronic structures. For all the transition bands observed, rotationally-resolved transition lines were fit to a theoretical model to retrieve molecular constants for both upper and lower electronic states. For the ScI molecule, seven vibrational bands of the D1П –X^1 Σ^+ system were recorded and analyzed. Accurate molecular constants for the v = 0 – 2 levels of the D^1П state and the v = 0 – 3 levels of the X^1 Σ^+ state were obtained. The equilibrium bond lengths, re (Å), for the electronic states of ScI were determined as follows: ScI X^1 Σ^+ D^1П r_e(Å) 2.6078 2.7146 For the ScBr molecule, three electronic transition systems were recorded and analyzed, which include six vibrational bands of the C^1 Σ^+– X^1 Σ^+ system, seven vibrational bands of the e^3Δ–a^3Δsystem and two vibrational bands of the d3Φ – a3Δ system. Rotationally resolved transition lines of both Sc79Br and Sc81Br isotopes were observed and analyzed. Least-squares fitting of the measured line positions yielded accurate molecular constants for the v = 0 – 2 levels of the X^1 Σ^+ state, the v = 0 – 3 levels of the C^1 Σ^+ state, the v = 0 and 1 levels of the d3Φ state and the v = 0 – 2 levels of both e3Δ and a3Δ states, respectively. The equilibrium bond lengths, re (Å), determined for electronic states of ScBr are given as follows: ScBr X^1 Σ^+ a^3Δ C^1 Σ^+ r_e(Å) 2.3806 2.4767 2.4776 A molecular orbital (MO) energy level diagram has been used to examine the electronic configurations giving rise to the different observed electronic states of ScI and ScBr. An attempt has been made to put the MOs of all the scandium monohalides under a single picture. A comparison of the molecular constants for the different electronic states of scandium monohalides indicates a weakening of the chemical bonding between the scandium atom and the halogen atoms down the group. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Thesis (PH. D.)--University of Pennsylvania, 1913.

No description available.

Here I report the hydrothermal chemistry of scandium, examining the behavior of the Sc³⁺ cation in various systems, including phosphates, phosphites, phosphonates and carboxylates. In total, 27 different materials, 23 of which are novel, have been synthesised and their structures solved. Seven different scandium phosphate-based materials have been successfully synthesised using amines and alkali hydroxides as structure directing agents, producing chain, layer and framework materials. Thermal analysis of these materials indicated that they were not stable upon removal of the template, because there are hydrogen bonding networks between the template and free OH groups on the phosphate groups. Certain conditions lead to the crystallization of either kolbeckite, Sc(PO₄).2H₂O, or a langbeinite-type structure, (NH₄)₂Sc₂(HPO₄)(PO₄)₂, which are dense frameworks. Investigation of scandium phosphites leads to the formation of more thermally stable frameworks. Investigation of scandium phosphite-based materials using different structure directing agents yielded three framework phosphite materials and one layered phosphite / phosphate. The use of lithium hydroxide and ethylenediamine within scandium phosphite systems resulted in the crystallization of a gainesite type framework, (LiSc(HPO₃)₂)and (H₃N(CH₂)₂NH₃)₂Sc₄(HPO₃)₈, which distorts in order to accommodate the amine, but not the lithium cation. Decreasing the potential for the formation of hydrogen bonding networks in the phosphite systems led to the formation of framework structures, however these structures did not retain their crystalline integrity upon removal of the template. In order to impart structure directing properties upon scandium-based materials but avoid the formation of hydrogen bonding networks upon which the crystalline integrity is dependent, scandium phosphonates were investigated. Seven different scandium phosphonate materials have been synthesised, two of which have been solved from powder diffraction data, and one from a combination of powder diffraction data, molecular modeling and single crystal data. Synthesis of scandium phosphonate materials yielded two thermally stable, porous materials with reversible water adsorption properties, NaSc(CH₃PO₃)₂•H₂O and Sc₂(O₃PCH₂(NHC₅H₁₀NH)₋CH₂PO₃)₃4H₂O. The success of this approach led to the examination of scandium carboxylate metal organic framework materials. The incorporation of Sc³⁺ into microporous carboxylate frameworks yielded three aliphatic scandium carboxylates and six aromatic scandium carboxylates. The scandium analogue of MIL-53 shows potential for gas adsorption studies, as well as illustrating that scandium carboxylates can be isostructural to metal carboxylate materials already published. The scandium terephthalate, Sc₂(O₂CC₆H₄CO₂)₃, is a small pore framework material with an unprecedented structure type, the adsorption properties of which have been examined using a variety of different small gas molecules and hydrocarbons, including X-ray analysis of the structures whilst adsorbing different molecules. ⁴⁵Sc MAS NMR has been performed on the materials prepared pure and characterized in this thesis, in order to establish a library of chemical shifts for scandium in different framework environments.

Thesis (Ph.D.)--Northwestern University, 2002. / Includes bibliographical references (leaves 191-202).

No description available.

Le massif du Koniambo fait partie d'un chapelet de massifs montagneux échelonnés le long de la côte ouest de l'île principale de Nouvelle-Calédonie. Il est un témoin de la grande nappe ophiolitique de Nouvelle-Calédonie mise en place à l'Éocène supérieur, dont l'élément principal est le Massif du Sud. Le massif du Koniambo comprend trois grands assemblages lithologiques et structuraux : a) l'assemblage basal à harzburgites et dunites serpentinisées de Vavouto; b) une séquence de dunites à chromite ; et c) une suite de nappes principalement à harzburgites +/- dunites dans la partie supérieure du massif. Ces assemblages surmontent l'Unité de Poya qui comprend, les volcanites à affinité BAB et MORB dans la plaine de Vavouto, la séquence de gabbros et dolérites de la région de Témala, les basaltes et pyroclastites de type OIB de la péninsule de Pinjen, et enfin les boninites de la plaine des Gaiacs au sud de la zone d'étude. L'enchevêtrement des unités volcaniques et volcano-sédimentaires de l'Unité de Poya à la base, surmontées par les gabbros de Témala et les unités mantelliques au sommet, suggère un assemblage imbriqué formant une suite structuralement inversée en provenance du bassin marginal Sud-Loyauté dont certains membres ultramafiques ont été fortement affectés par leur passage en milieu supra-subductif (SSZ). La spécificité des péridotites du Koniambo et des séquences volcaniques sous-jacentes apparaît en premier lieu le résultat d'une double fusion partielle des péridotites ; • La première phase de fusion, réalisée du Crétacé supérieur au Paléocène lors de l'ouverture du bassin marginal Sud-Loyauté, serait à l'origine des basaltes océaniques de type MORB de l'Unité de Poya. Des processus annexes ont alors conduit à la formation d'OIB et de BAB dans le contexte océanique du bassin Sud-Loyauté. • La seconde phase de fusion à l'Éocène, serait liée à la subduction de la lithosphère des Loyauté sous le proto-arc du même nom. Elle pourrait expliquer l'origine des boninites alors formées en position d'avant-arc et le caractère extrêmement appauvri en REE des harzburgites. De manière complémentaire, les assemblages antigorite/lizardite et chrysotile/magnétite de la séquence basale de Vavouto suggèrent un processus multiphasé d'altération hydrothermale dont une partie pourrait avoir été réalisé à relativement faible profondeur dans le coin mantellique supra-subductif au-dessus de la lithosphère plongeante des Loyauté puis lors de la remontée des matériaux concernés et de l'obduction des péridotites. Des précipitations de giobertite et une imprégnation siliceuse des matériaux d'origine incertaine affectent également les matériaux. L'assemblage structural du massif du Koniambo sur le socle de la Nouvelle-Calédonie apparait quant à lui le résultat de trois évènements tectoniques. - L'obduction à l'Éocène supérieur de la séquence croûte océanique/nappe ophiolitique sur le bâti Calédonien qui a provoqué l'accrétion d'écailles mantelliques selon une disposition apparente inversée dans le massif du Koniambo. L'étude des indicateurs cinématiques confirme que la séquence ophiolitique fut obductée en provenance du N/NE. - la subduction avortée vers l'ouest de la lithosphère du bassin de Nouvelle-Calédonie sous le bâtit calédonien, entrainant la formation de failles NE et le découpage de la séquence ophiolitique en sept domaines structuraux distincts. - La formation au nord et nord-est de la zone, d'une faille de coulissage, désignée « l'Accident Tectonique Majeur, ATM ». Cette dernière présente un corridor de déformation en transpression présentant des rampes de chevauchement frontales ainsi que de coulissage oblique-dextre, l'ensemble est fortement incliné vers le nord-est. Des failles normales, présentes principalement sur les versants ouest des massifs du Koniambo et du Katépahie, traduiraient les effets de l'ajustement isostatique de la ride de Norfolk suite au détachement en profondeur de la nappe subductée combiné à la surélévation du socle de la Nouvelle-Calédonie. En ce qui concerne les mécanismes d'altération supergène en milieu tropical, la présence de garniérite dans des saprolites comportant une forte proportion de serpentines primaires résiduelles est synonyme d'un enrichissement en nickel via les processus de latéritisation. Les travaux effectués sur le massif du Koniambo ont permis d'identifier certains niveaux d'enrichissements en scandium dans les phases minéralogiques des altérites. Il est ainsi observé que le scandium est relativement immobile dans un environnement d'altération latéritique et, par conséquent, se concentre dans les faciès résiduels augmentant ainsi sa teneur dans une proportion identique, mais inverse à la perte de volume et de densité du matériel latéritique résiduel. Une méthodologie de modélisation tridimensionnelle de la répartition des teneurs en nickel, cobalt et autres oxydes dans les gisements latéritiques est présentée. Celle-ci met en œuvre les principes de géostatistique tels que le kriging pour l'interpolation des blocs en milieu déridé (unwrinkling), ainsi que le concept de changement de support afin d'adapter le modèle à la sélectivité minière envisagée. Une méthode de classification des ressources minières en fonction des risques associés à la variabilité dans la distribution de la teneur en nickel ainsi que de l'épaisseur des séquences minéralisées est présentée.