A range of fluorescein derivatives were synthesised via Pd0-mediated cross-coupling chemistry of the mono triflate of fluorescein with a variety of boronic acids and the optical properties of each dye was studied. Among these derivatives, a new multicolour pH–dependant anthofluorescein which was highly sensitive to pH changes and viscosity changes was identified. Work was carried out to explore intracellular catalysis based on the immobilisation of Pd0 nanoparticles on microspheres. The entrapped Pd0 nanoparticles were rapidly taken up by cells, stay harmlessly within the cytoplasm for days and were shown to carry out novel cell-based chemistry. This included an allylcarbamate cleavage and a Suzuki-Miyaura cross-coupling reaction for the in situ generation of a mitochondria-localized “switch-on” fluorophore.

Thesis (M.Sc.)--University of the Witwatersrand, Faculty of Science, School of Chemistry, 2017. / In this work, commercially relevant palladium catalysed direct arylation reactions, in which the molecule oxazole is coupled to toluene were investigated computationally. These involve the Pd(II)/Pd(0) manifold. Each of the three hydrogen atoms of oxazole can be replaced by a toluene molecule, and as both mono- and di-substitution occurs there are 6 possible products. Experimental results, using the catalyst Pd(OAc)2 in DMA solvent, show that both the presence and quantity of tri-tertiary butyl phosphine (PtBu3) ligand has a significant impact on the observed product distributions. The aims of this study were to discover why and to ascertain the rate determining step (RDS) of the catalytic cycle under various conditions. All geometry optimisation and frequency calculations were conducted using the TPSSh hydrid DFT functional in conjunction with the Def2-SVP basis set. Single point energy benchmarks at the DLPNO-CCSD(T)/Def2-TZVP level of theory revealed that the double hybrid (DH) functional DSDPBEP86 in conjunction with the Def2-TZVP basis set was the best compromise between accuracy and efficiency for the systems at hand. The generally accepted concerted metallation deprotonation(CMD) mechanism was investigated under phosphine free conditions, where a DMA solvent molecule was modelled bound to the palladium centre. The results correctly predicted the experimental product distibutions for both mono- and di-substitution. The CMD mechanism was also investigated under conditions of 1 equivalent of PtBu3 ligand. In this case a PtBu3 molecule was modelled bound to the palladium centre. The results correctly predicted the major mono-substituted experimental product and from the data formation of the major disubstituted product was readily rationalized. Finally, oxidative addition (OA) was investigated under both conditions. It was found that the COSMO solvation model had a dramatic impact on OA reaction Gibbs energies. It was discovered that the presence of PtBu3 ligand significantly reduced the total Gibbs energy required for OA. In the absence of PtBu3, no DMA is coordinated to the palladium centre during OA. Regeneration of the active Pd(II) catalyst via deprotonation was the modelled completing the entire catalytic cycle. The RDS under phosphine free conditions was calculated to the CMD transition state (TS). Under condition of 1 equivalent of PtBu3 ligand the RDS was a mixture of both the CMD TS as well as coordination of oxazole to the active Pd(II) catalyst. / LG2018

1. É relatado estudo sistemático da extratibilidade de complexos mistos de metais de transição com haletos, pseudohaletos e trifenilfosfina, arsina, estibina, sob condições variadas, com diversos solventes, mostrando as tendências gerais de comportamento das espécies envolvidas. Dessa ampla abordagem derivam algumas possibilidades de aplicações analíticas que são desenvolvidas. 2. A presença de cianeto impede a formação e destrói alguns complexos de paládio do tipo acima referido, fato que conduziu à elaboração de uma prova de toque para este íon. Papel convenientemente preparado, contendo complexo de paládio, é descorado por HCN desprendido de amostras contendo cianeto, possibilitando a identificação de 0,3 µg de CN. Na presença de interferentes, algumas modificações de procedimento tornam o teste praticamente específico. 3. A partir de soluções aquosas contendo o ácido hacloroplatínico (IV), soluções benzênicas de trifenilestibina somente extraem o produto organometálico na presença de iodeto e não de brometo ou cloreto. As condições para uma extração seletiva e subsequente determinação espectrofotométrica de iodeto são indicadas, assim como as tolerâncias para outros íons estranhos. O método elaborado permite identificar iodeto na faixa de concentração de 6 - 24 ppm na diluição final, sendo a medida espectrofotométrica efetuada em 385 nm. 4. O complexo diazido-bis(trifenilfosfina)-paládio (II), em solução benzênica, reage com monóxido de carbono dando o isocianeto complexo correspondente, com mudança das características espectrais região do ultravioleta próximo. Com base nesta reação, mostra-se que possível a determinação espectrofotométrica de monóxido de carbono misturas gasosas com teores 700 - 3000 ppm. / Abstract not available.

by Yip Yeuk Lan = 已發生液態調幅分離的過冷「鈀八十二硅十八」合金熔融體的結晶行為 / 葉若蘭. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 51-52). / Text in English; abstracts in English and Chinese. / by Yip Yeuk Lan = Yi fa sheng ye tai diao fu fen li de guo leng "ba ba shi er gui shi ba" he jin rong rong ti de jie jing xing wei / Ye Ruolan. / Acknowledgments --- p.ii / Abstract --- p.iii / 摘要 --- p.iv / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Introduction / Chapter 1.2 --- Properties of Nanocrystalline Materials / Chapter 1.3 --- Fabrication of Nanocrystalline Materials / Chapter 1.4 --- Fabrication of Nanocrystalline Material by Spinodal Decomposition / Chapter 1.5 --- Aim of the Thesis / References / Figures / Chapter Chapter 2 --- Experimental --- p.28 / Chapter 2.1 --- Introduction / Chapter 2.2 --- Preparation of Fused Silica Tubes / Chapter 2.3 --- Sample Preparation / Chapter 2.4 --- Sample Preparation for Microstructure Analysis / Chapter 2.5 --- Microstructure Characterization by TEM / Chapter 2.6 --- Annealing a TEM sample / References / Figures / Chapter Chapter 3 --- Results and Discussions --- p.44 / Results / Discussions / References / Figures

Lee Ka-lun. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references. / Acknowledgments --- p.ii / Abstract --- p.iii / Table of Contents --- p.v / Chapter Chapter 1: --- Introduction --- p.1 / Chapter 1.1 --- Phase Separation in Glass-Forming Alloys --- p.2 / Chapter 1.1.1 --- Metallic Glass --- p.2 / Chapter 1.1.2 --- Phase Separation in Metallic Glasses --- p.3 / Chapter 1.1.3 --- Phase Separation in the Undercooled Melts of Glass-Forming Alloys --- p.4 / Chapter 1.2 --- Theory of Phase Separation --- p.5 / Chapter 1.2.1 --- Thermodynamics of Phase Separation --- p.5 / Chapter 1.2.2 --- Phase Separation by Nucleation and Growth --- p.7 / Chapter 1.2.3 --- Cahn's Theory of Spinodal Decomposition --- p.8 / Chapter 1.3 --- Experimental Method to Achieve High Undercooling --- p.11 / References --- p.14 / Figures --- p.15 / Chapter Chapter 2: --- Phase Separation in Undercooled Molten Pd80Si20 --- p.23 / Abstract --- p.24 / Introduction --- p.25 / Experimental --- p.29 / Results --- p.30 / Discussions --- p.36 / References --- p.45 / Figures --- p.47 / Chapter Chapter 3: --- Metastable Liquid Phase Separation in Undercooled Molten Pd40.5Ni40.5P19 --- p.60 / Abstract --- p.61 / Introduction --- p.62 / Experimental --- p.62 / Results and Discussions --- p.63 / References --- p.68 / Figures --- p.69 / Chapter Chapter 4: --- Crystallization of Spinodal Decomposed Melts of Pd80Si20 --- p.74 / Introduction --- p.75 / Experimental --- p.76 / Results --- p.77 / Discussions --- p.80 / References --- p.84 / Figures --- p.85

Disposal of chlorinated hydrocarbons is a major environmental concern due to the lack of a satisfactory means of safe remediation at all contaminated locations. Current technologies rely primarily on incineration, a process that can lead to dangerous byproducts such as dioxin. If the chlorine substituent can be removed prior to incineration, or other disposal method, the subsequent steps of disposal pose less of an environmentally risk. The catalyst developed in this study is designed to promote the dechlorination reaction. A methodology for the production of a palladium based metal support catalyst is presented. This technique allows the palladium catalyst to be deposited on a copper metal surface. The catalyst is active in the dechlorination of p-chlorophenol, which is used as model molecule representing a range of chlorinated phenolic compounds. Hydrogen is used in the concert with catalyst to affect the dechlorination. Chemical process rates of 0.3-1.0 cm³/g*s are observed. / Graduation date: 2001

Graduation date: 2002

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 126-127).

Our group has developed a strategy for the synthesis of benzofused carbocycles and heterocycles through tandem palladium-catalyzed reactions of gem-dibromoolefins. In these syntheses, one bromide undergoes a Pd-catalyzed cyclization reaction, and the other participates in an orthogonal inter- or intramolecular Pd-catalyzed reaction to functionalize or annulate that ring, respectively. Chapter 1 describes the pairing of an intramolecular C–N bond forming reaction (the Buchwald-Hartwig coupling) with an intramolecular direct arylation for the synthesis of fused indole derivatives. A range of previously unknown heterocycles were synthesized through this method. Chapter 2 describes the synthesis of benzothiophenes through the combination of a Pd-catalyzed C–S coupling with an orthogonal Suzuki, Heck, or Sonogashira reaction. This represents the first example of the incorporation of Pd-catalyzed C–S coupling into a tandem reaction. In Chapter 3, a tandem intramolecular Heck / intermolecular Suzuki reaction is described for the synthesis of methyleneindenes. Studies on this reaction have provided advanced understanding of the mechanism, including how variation of the ligand controls the regioselectivity of the reaction.

Our group has developed a strategy for the synthesis of benzofused carbocycles and heterocycles through tandem palladium-catalyzed reactions of gem-dibromoolefins. In these syntheses, one bromide undergoes a Pd-catalyzed cyclization reaction, and the other participates in an orthogonal inter- or intramolecular Pd-catalyzed reaction to functionalize or annulate that ring, respectively. Chapter 1 describes the pairing of an intramolecular C–N bond forming reaction (the Buchwald-Hartwig coupling) with an intramolecular direct arylation for the synthesis of fused indole derivatives. A range of previously unknown heterocycles were synthesized through this method. Chapter 2 describes the synthesis of benzothiophenes through the combination of a Pd-catalyzed C–S coupling with an orthogonal Suzuki, Heck, or Sonogashira reaction. This represents the first example of the incorporation of Pd-catalyzed C–S coupling into a tandem reaction. In Chapter 3, a tandem intramolecular Heck / intermolecular Suzuki reaction is described for the synthesis of methyleneindenes. Studies on this reaction have provided advanced understanding of the mechanism, including how variation of the ligand controls the regioselectivity of the reaction.