A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry. Johannesburg, 2013 / Unable to load abstract.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. Johannesburg, 2016. / In this PhD thesis, the synthesis, crystal chemistry and thermoresponsive behaviour of non-porous borophosphates [ABPO5 (A= Ca, Sr, Ba) and BPO4] and porous borophosphates [NH4Fe(III)[BP2O8(OH)] and MIxMIIz(H2O)2[BP2O8].zH2O (MI = Na, NH4 and MII = Mn, Co)] phases were investigated. Understanding the crystal structure dynamics as a function of temperature of the selected porous and non-porous borophosphates revealed the thermal stability of the studied compounds, while serving as a predictive measure of the effects of temperature on other materials properties and subsequent applications. The non-porous borophosphates were synthesized using the solid state method, whereas the porous borophosphates were synthesized using the hydrothermal method. The powder X-ray diffraction (PXRD) technique, along with the application of the Rietveld refinement method, was the principle characterisation technique employed for the non-destructive and non-invasive thermoresponsive characterisation of the studied borophosphate phases. This thesis consists of seven chapters, four of which are independent papers corresponding to four chapters. Chapter 1 reviews the relevant scientific literature, while chapter 2 describes the methods of characterisation used in this thesis. Concerning the highly thermally stable non-porous borophosphates, chapter 3 presents the thermal expansion behaviour of ABPO5 compounds, which have been determined from the sequential application of the Rietveld refinement method of variable temperature powder X-ray diffraction (VT-PXRD) data. For trigonal ABPO5 compounds, a near linear expansion of the unit cell axes was found for all structures as a function of temperature. The variation of the crystal structure with temperature of ABPO5 compounds was also established. With the general understanding that borophosphates display intriguing crystal structure architectures, chapter 4 describes the synthesis and characterisation of four metal borophosphate hydrates: NaMII(H2O)2[BP2O8](H2O); MII = Co (I), Mn (II) and (NH4)0.5MII1.25(H2O)2[BP2O8](H2O)0.5; MII = Co (III), Mn (IV). The structures refined at room temperature from PXRD data revealed that isostructural phases I and II have an ordered arrangement of water molecules in the voids, whereas isostructural phases III and IV have fractional and disordered distribution of water molecules in the voids. Scanning electron microscope (SEM), fourier transform infrared spectroscopy (FT-IR), variable temperature powder X-ray diffraction (VT-PXRD) and thermogravimetric analysis (TGA) for all compounds are also presented. Chapter 5 was an investigation into the synthesis, crystal structure and thermal properties of the porous iron borophosphate NH4Fe(III)[BP2O8(OH)]. Variable temperature PXRD and thermogravimetric analysis were used to investigate the compounds thermal stability and expansion behaviour. Thermal investigations indicated that the compound is stable up to 470 °C. Of great importance to the accurate and/or precise measurement of the crystal structures and lattice parameters of the phases investigated using powder diffraction was the correct application of the Rietveld refinement method to the measured diffraction data. Therefore, chapter 6 is an investigation into a number of different Rietveld refinement approaches, which were aimed at modelling the changes in the atomic coordinates of BPO4 as a function of temperature. Parametric Rietveld refinements and rigid body Rietveld refinements were among the refinement strategies employed. / LG2017

Thesis advisor: Shih-Yuan Liu / The first three chapters of this dissertation elaborate on certain facets of the isosteric relationship between different types of boron-nitrogen-containing heterocycles and the corresponding all-carbon compounds. In this vein, Chapter 1 describes selective photoisomerization of aromatic 1,2-dihydro-1,2-azaborines to BN-analogues of bicyclo[2.2.0]hexa-2,5-diene (Dewar benzene). In one instance, the photoisomer product was further derivatized into a series of disubstituted cyclobutanes through manipulations of the boron functionality. Chapter 2 discloses a combined experimental/theoretical mechanistic investigation of preliminary hydrogen release from the amine borane unit in a pair of BN-cycloalkanes. In Chapter 3, the kinetics of complementary dehydrogenation of the alkyl units in a BN-cyclohexene derivative are compared with those of related six-membered carbocycles. Chapter 4 treats with the separate subject of enantioselective silylation of glycerol by a catalytic strategy centered around reversible covalent binding of substrate hydroxyl groups. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Amir H. Hoveyda / Chapter 1. Efficient Z-Selective Synthesis of Allylic- and Alkenyl Boronates by Catalytic Cross-Metathesis Efficient Z-selective cross-metathesis reactions to furnish Z-(pinacolato)-allylboron and Z-(pinacolato)alkenylboron compounds through catalytic cross-metathesis are disclosed. Z-allylic boron compounds are generated by the use of catalytic amounts of a W-based monoaryloxide monopyrrolide (MAP) complex in up to 91% yield and 96:4 dr after allylation to benzaldehyde. Alkenylboron compounds are prepared in high yields and high Z selectivity in up to 93% yield and 97:3 Z:E. Cross-metathesis reactions with 1,3-dienes and aryl olefins are efficient and highly Z-selective. Combination of cross-metathesis and cross-coupling to synthesize anticancer agent combretastatin A-4 highlights the utility of this approach. Chapter 2. Synthesis of Macrocyclic and Acyclic Z-Enoates and (E,Z) or (Z,E) Dienoates by Catalytic Cross-Metathesis The first examples of kinetically controlled catalytic olefin metathesis reactions to generate Z-α,β-unsaturated macrocyclic and acyclic esters are disclosed. The synthesis of (E,Z) or (Z,E)-dienoates are also presented. Reactions promoted by 3.0–10 mol % of Mo-based monoaryloxide monopyrrolide complex proceed to completion to the desired macrocycles within 2–6 h at room temperature. Macrocycles of diverse ring sizes are formed in 79:21 to >98:2 Z:E selectivity. Pure Z isomers can be obtained after purification in up to 75% yield. Acyclic Z-α,β-unsaturated esters are prepared in the presence of acetonitrile to avoid using excess amounts of the more valuable cross-partner substrate. Spectroscopic investigations and X-ray analysis rationalize the positive effect of acetonitrile in the reaction system. Linear (Z)-enoates are generated in up to 71% yield and up to >98:2 Z:E. (E,Z)-Dienoates are generated with high Z selectivity as well. The utility of the ring-closing metathesis and cross-metathesis is highlighted by the synthesis of an (+)-aspicilin precursor and the C1–C12 fragment of biologically active natural product (–)-laulimalide. Chapter 3. Application of E-Selective Catalytic Ring-Closing Metathesis in the Total Synthesis of Dolabelides A, B, C and D Efforts towards the enantioselective synthesis of the dolabelide family of anti-cancer macrolides is presented. Development of a total synthesis incorporating a late-stage kinetically E-selective RCM is illustrated. Previous attempts to synthesize the macrolide by ring-closing metathesis (RCM) have demonstrated poor efficiency and low selectivity for the E isomer. Methodology developed in our group with acyclic trisubstituted cross-metathesis demonstrates that high selectivity can be achieved with stereodefined 1,2-disubstituted and trisubstituted olefins by the use of the proper catalyst and reaction design. Modern catalytic and stereoselective approaches towards the two main fragments of dolabelide are presented. More efficient and concise routes will be pursued to highlight the utility of the proposed disconnections and practicality of the total synthesis / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: James P. Morken / This dissertation details the development of several enantioselective or stereospecific transformations involving organoboronic esters. Chapter one will introduce electrophile-induced boronate rearrangements which underpins much of the reactivity that will be discussed in subsequent chapters. In chapter two the conjunctive cross-coupling reaction is presented. Its development and application to the synthesis of non-racemic boronic esters, along with its application to the synthesis of enantioenriched allylic boronic esters, will be discussed. In chapter three the cross-coupling of geminal bis(boronic) esters is introduced and the development of a method to employ them in cross-coupling with alkenyl bromides, affording enantioenriched substituted allylic boronic esters is outlined. In chapter four we highlight the utility of allylic boronic esters, and detail the development of a cross-coupling reaction that involves the use of these substrates and halide electrophiles to furnish enantiomerically enriched products containing all carbon quaternary stereocenters. Finally, in chapter five we describe the development of a metalfree amination reaction of organoboron compounds, which is able to deliver otherwise difficult-to-access enantiomerically enriched α-tertiary amines. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2016. / Boron concentration analysis is an important and critical analysis performed by the Analytical Chemistry Laboratory at Koeberg Nuclear Power Station (KNPS), because boron controls reactivity and the concentration determination is a Technical Specification Parameter (safety parameter). Hence accurate, precise results for boron concentration produced by laboratories and on-line analysers are important because of their operational implications associated with reactivity control and also for nuclear safety. The project focused on comparing the quality of chemical analysis results of boron produced by analysis techniques/ methods used at Koeberg Nuclear Power Station namely; Potentiometric Titration, Atomic Absorption Spectrophotometry (Flame) and UV-VIS Azomethine-H method. The methods were described, optimised, evaluated and compared in terms of uncertainty of measurement, accuracy, precision, analysis range, limitations, appropriateness and applicability for boron analysis in 2500 mg B/kg concentration range. For Potentiometric Titration method, the measurement uncertainty = 2500 ±16 mg B/kg, accuracy= 0.2%, precision= 0.08% the range of analysis= 5-800 mg B/kg. For Atomic Absorption Spectrophotometry (Flame) the measurement uncertainty= 2500 ±51 mg B/kg, accuracy= 0.12%, precision= 0.44% the range of analysis= 0 -500 mg B/kg. For UV-VIS Azomethine-H the measurement uncertainty= 2500 ±72 mg B/kg, accuracy= 0.08%, precision= 0.44% the range of analysis= 0 -10 mg B/kg. The INPOs 95% accuracy and precision criteria for boron is ± 1%. So these techniques could be used for boron analysis in PWR. Based on the evaluation and assessments mentioned above; the Potentiometric Titration was found to be the most preferred method for boron analysis for Pressurised Water Reactors followed by Atomic Absorption Spectrophotometry (Flame) that can be of good use in determining boron especially in waste samples and samples with complex matrices. The UV-VIS Azomethine-H methods can only be used when it is really necessary to determine very low levels of boron between 0- 10mg B/kg of which it was never required before. Since it is specifically the B-10 isotope that is responsible for the ability to control reactivity, the implementation of isotopic boron analysis (by Inductively Coupled Plasma – Mass Spectrometry) at KNPS is explained and the advantage of the programme is illustrated. Although the current state of instrumental capabilities is adequate for 10B isotope determination, further work of optimising the methodology for even better results is recommended.

The development of safe and efficient hydrogen storage materials will aid in the transition away from fossil fuels toward a renewable, hydrogen-based energy infrastructure. Boron-nitrogen (BN) containing materials have attracted much attention due to their high hydrogen storage capacity and fast kinetics of hydrogen release. Furthermore, computational studies predict that hydrogen storage materials based on the BN-heterocycle 1,2-azaborine may enable reversible H2 uptake and release, with little additional energy input. This thesis develops the basic science needed for a hydrogen storage platform based on BN-heterocycles such as 1,2-azaborine. Chapter I is a review of recent developments in azaborine chemistry. Chapter II describes a regeneration scheme from a "spent" 1,2-azaborine hydrogen storage material to "fully charged" fuel using molecular H2 and H-/H+ equivalents. Chapter III describes the experimental determination of the resonance stabilization energy of 1,2-azaborines using reaction calorimetry. Chapter IV explores the effect of boron-substitution on the rate and extent of hydrogen release from BN materials. Chapter V describes work on a project unrelated to hydrogen storage, the synthesis and electronic parameter determination of the first 1,2- azaborine-containing phosphine ligand analog. This dissertation includes previously published and unpublished co-authored material.

Reverse Osmosis membranes have been successfully proven to remove almost 99% of chemicals dissolved in seawater. However, removal of certain trace elements, such as boron is challenging and relatively low for seawater reverse osmosis desalination plants compared to thermal desalination plants. Boron is naturally occurring and is present in seawater at an average concentration of 4.5-5 mg/L. While boron is a vital element, its toxicity has been proven on crops, animals and possibly humans. Additionally, boron should be removed to comply with the current guideline value of 0.5 mg/L, for drinking water, issued by the World Health Organization (WHO), which is barely attained by a single-pass process seawater reverse osmosis plant. Currently, multipass reverse osmosis membrane operations with pH modifications are the only valid method for boron removal. However, this is not economically efficient as it requires higher energy and chemicals consumptions. The objective of this study was to investigate boron removal by commercial TFC RO membranes in addition to custom-made KAUST-synthesized TFC membrane. Five membrane samples were examined: Toray, Sepro, Koch, and KAUST in-house synthesized membrane. Three different feed pH conditions were used: pH6, pH8, and pH10. Filtration experiments were conducted in two parts. In experiment 1, all five membranes were examined for boron rejection in a dead-end permeation system, whereas in experiment 2 the two membranes with the highest boron rejection from experiment 1 were tested in a cross-flow system. Permeate and feed samples were taken continuously and analyzed for boron concentration, rejection calculation. Membrane surfaces were characterized according to hydrophilicity, roughness and surface charge. The results showed for all the tested membranes that boron rejection increased as the feed pH increased. KAUST, defect-free TFC, showed the highest performance for boron rejection for all pH conditions, although, it shows the roughest surface. Toray membranes 80LB and 80B exhibited the second highest boron rejection and had the most negatively charged membrane surfaces. It was observed in this study that the rejection of boron by a membrane is due to size exclusion and charge repulsion mechanisms. It was concluded that, the KAUST, defect free TFC has the potential to be applicable for boron rejection in industrial application as it has better boron rejection than commercially available RO membranes.

Layered van der Waals materials have played a pivotal role in expanding the scope of condensed matter physics by examining the effects of reduced dimensionality in various systems. These include semiconductors, ferromagnets, and charge density wave materials, among many others. Hexagonal boron nitride (hBN) is often used as a passivation/encapsulation layer for air-sensitive materials in optical and electronic studies owing to its effectiveness as a substrate for graphene in transport measurements. In this thesis, samples probed by Raman spectroscopy and as well as those measured through electronic transport were first encapsulated during fabrication. The specific experimental details are found in each corresponding chapter. This thesis aims to characterize several 2-D materials and explore physical phenomena arising from combinations thereof through optical and electronic means. Before delving into the specific research projects, it provides a motivation for each, descriptions of the material(s) involved, and sample fabrication techniques used to assemble the various heterostructures. Topics to be covered include the effects of encapsulation on the transition metal dichalcogenide (TMD) 1T’-MoTe2 subject to elevated temperatures, how the nearly commensurate to commensurate phase transition of another TMD, the charge density wave material 1T-TaS2, in its few-layer form can be tuned electronically, preliminary results of electronic transport in graphene-ferromagnet heterostructures, and an outline of other optical studies on mono- to few-layered forms of related materials and possible future directions that may be pursued.

Boron nitride (BN) materials have unique properties, which has led to interest in them in the last few years. The deformation of boron nitride materials including hexagonal boron nitride, boron nitride nanosheets (BNNSs) and boron nitride nanotubes have been studied by Raman spectroscopy. Both mechanical and liquid exfoliations were employed to obtain boron nitride nanostructures. Boron nitride glass composites were synthesised and prepared in thin films to be deformed by bending test in-situ Raman spectroscopy. Hexagonal boron nitride in the form of an individual flake and as flakes dispersed in glass matrices has been deformed and Raman measurement shows its response to strain. The shift rates were, -4.2 cm-1/%, -6.5 cm-1/% for exfoliated h-BN flake with thick and thin regions and -7.0 cm-1/%, -2.8 cm-1/% for the h-BN flakes in the h-BN/ glass (I) and glass (II) composites. Boron nitride nanosheets (BNNSs) shows a G band Raman peak at 1367.5 cm-1, and the deformation process of BNNSs/ glass composites gives a shift rate of -7.65 cm-1/% for G band. Boron nitride nanotubes (BNNTs) have a Raman peak with position at 1368 cm-1, and their deformation individually and in composites gives Raman band shift rates of -25.7 cm-1/% and -23.6 cm-1/%. Glass matrices shows compressive stresses on boron nitride fillers and this was found as an upshift in the frequencies of G band peak of boron nitride materials. Grüneisen parameters of boron nitride (BN) were used to calculate the residual strains in glass matrices of BNNSs nanocomposites as well as to estimate the band shift rates which found to be in agreement with the experimental shift rate of bulk BN and BNNTs.