The ability of a deprotonated aza-crown ether to allow isolation of soluble lanthanide and yttrium complexes has been investigated. A convenient route to these complexes has been demonstrated by the protonolysis reactions of Ln[(N(SiMe₃)₂]₃ with 4,13-diaza-18-crown-6. NMR spectroscopy and X-ray crystallography revealed a C₂V structure consisting of a basket shaped geometry. The successful protonolysis route has been extended to the preparation of stable alkyls, dialkyls, and alkyl cations of yttrium and zirconium stabilized by deprotonated aza- crown macrocycles. A yttrium, alkyl complex containing deprotonated diaza-18-crown-6 has been prepared by the protonolysis route. The thermal stability and reactivity of this complex were investigated. This alkyl reacts with terminal alkynes to produce a complex equilibrium between the colourless monomeric and dimeric alkynides and a purple Z-butatrienediyl (ie.RC=C=C=CR²⁻) coupling product. NMR studies demonstrate that electron poor alkynes favour coupling and that the carbon-carbon double bond forming process is readily reversible at room temperature. The flexibility of the deprotonated diaza-crown ligand is apparent from the isolation of both cis and trans-zirconium dibenzyl complexes from the protonolysis of tetrabenzyl zirconium with 4,13-diaza-18-crown-6. The structure of both isomers were investigated by NMR spectroscopy and X-ray crystallography. Both the cis and trans-isomers cleanly converted to the stable cation either by protonolysis with [n-Bu₃NH]⁺[BPh₄]⁻ or by alkyl abstraction with B(C₆F₅)₃. The reactivity of the alkyl cation derived from the reaction with B(C₆F₅)₃ was investigated. The reaction of this cation with t-BuNC gave a vinylamide complex following a 1,2-proton rearrangement of an initially formed iminoacyl. Two members of the still rare yttrium dialkyl class of compounds were isolated using monoanionic, deprotonated aza-crown ethers as supporting ligation. The dialkyl complexes were synthesized by protonolysis of Y(CH₂SiMe₃)₃(THF)₂ with either aza-18-crown-6 or aza-15-crown-5. NMR and X-ray analyses of the yttrium dialkyl supported by aza-18-crown-6 indicates a trans-dialkyl geometry while NMR analysis of the aza-15-crown-5 analog indicates a cis-dialkyl geometry. Reaction of the trans-dialkyl complex with CO afforded a trans-dienolate complex formed by the migration of SiMe₃. Alkyl abstraction from the trans-dialkyl complex using B(C₆F₅)₃ allowed generation of the first yttrium, alkyl cation. / Graduate

M.Sc. / Please refer to full text to view abstract

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Galactitol and cis,cis,cis-1,3,5-cyclohexanetriol are polyols that are ideal examples of model compounds for ligands with lanthanide ions as they have their hydroxyl groups in favourable steric arrangement. Several complexes were synthesised with both lanthanide chloride and lanthanide nitrate salts with galactitol, and a variety of structures, both polymeric and monomeric, were observed. In all these complexes, galactitol acted as a bridging molecule between the lanthanide ions. A notable difference was the lanthanum chloride–galactitol complex that showed both chloride and galactitol bridging. The lanthanide nitrate salts formed only polymeric complexes with galactitol. Not all of the complexes showed nitrate ions coordinated to the metal centre, and in the neodymium nitrate– galactitol complex, which shows both monodentate and bidentate coordination of the nitrate groups. The coordination of the nitrate ions was confirmed using both XRD and IR analysis. Two complexes with lanthanide chloride salts and cis,cis,cis-1,3,5-cyclohexanetriol were synthesised and analysed. Lanthanum chloride formed a polymeric complex, which showed extensive chloride bridging between the metal centres. Praseodymium chloride formed a dimeric complex. All complexes were analysed with single-crystal X-ray diffraction, 1H NMR, 13C NMR and IR spectroscopy.

The three terminal capacitance dilatometer is the most sensitive means for measuring the thermal expansion of solid samples at low temperatures. A measuring system based around capacitance dilatometry has been automated to provide a means of routine data collection of length changes in samples in the temperature range 1.5 K to 300 K. The dilatometer has been used in conjunction with magnetisation and neutron scattering measurements to investigate members from rare earth alloys as part of a wider study of the magnetic and lattice properties of isostructural rare earth alloy series, in particular the rare earth alloy series RE2AgIn (RE = Tb, Ho and Er) and REPtIn (RE = Nd, Gd, Tb, Dy, Ho and Er). Two samples have been investigated using thermal expansion, Tb2AgIn and TbPtIn. Both order magnetically at temperatures around 50 K and phase transitions corresponding to the ordering were observed using the capacitance dilatometer for the samples. The data for the alloy series is presented and discussed with a view to describing the complex nature of these alloy systems.

Magnesium has the lowest density of any structural metal making it a strong candidate for weight savings in the aerospace and automotive industries. However, strong crystallographic textures combine with anisotropic deformation modes to severely limit formability in wrought magnesium alloys. Recently improved formability has been achieved by the addition of small concentrations of solute rare earth elements which reduce the intensity of recrystallisation textures. Developing a mechanistic understanding of this effect is critical in leading alloy design towards a new class of highly formable wrought magnesium alloys. In this study the static recrystallisation mechanism of rolled magnesium rare earth alloys, which causes the texture weakening, is examined with a particular emphasis on the contrasting texture weakening effects in binary and tertiary magnesium rare earth alloys. In binary magnesium-rare earth alloys the `rare-earth' texture is simply a weakened deformation texture, while recrystallisation of magnesium-zinc-rare earth alloys produces unique `rare-earth' texture components. In the binary alloys weakened recrystallisation textures are attributed to the generation of `off-basal' orientations within regions of high strain localisation during deformation. These orientations recrystallise and subsequently dominate the recrystallised texture. Texture weakening by this mechanism is also thought to be observed in non-rare earth magnesium alloys where dynamic recrystallisation is suppressed by cold rolling. The unique rare-earth texture components in magnesium-zinc-rare earth alloys are found to be determined by the orientation of shear bands in the material. Similarly to texture weakening in the binary alloys, nuclei for these orientations are thought to develop during deformation as a result of strain incompatibilities within shear bands. The mechanism forming these orientations remains unclear, however it is postulated that a complex change in recovery behaviour within shear bands, as a result of rare earth and zinc additions, may be the cause. Retarded dynamic recrystallisation is suggested to be of critical importance in the texture weakening mechanisms of all magnesium alloys, both rare earth and non-rare earth. In rare earth alloys dynamic recrystallisation is suppressed by the segregation of rare earth atoms to grain boundaries. A combination of high resolution TEM and EDX shows rare earth atoms form clusters approximately 2nm in diameter on grain boundaries which are expected to retard dynamic recrystallisation through a solute drag mechanism.

Ph.D. (Physics) / Please refer to full text to view abstract