Thesis (Ph. D.)--University of Wisconsin--Madison, 1985. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 178-189).

Berlin, Humboldt-University, Diss., 2003.

Berlin, Freie Universiẗat, Diss., 1998. / Dateiformat: zip, Dateien im PDF-Format.

Berlin, Universiẗat, Diss., 2001. / Dateiformat: zip, Dateien im PDF-Format.

The preparation and reactions of simple and complex fluorides of palladium and gold using fluoride solvents have been studied. Two new compounds, fluoselenonium hexafluopalladate (IV) and fluoselenonium tetrafluoaurate (III), have been prepared. Both are acids in the selenium tetrafluoride solvent system. Fluoselenonium hexafluopalladate (IV) reacts with a base, potassium pentafluoselenate (IV), to form a salt, potassium hexafluopalladate (IV) which crystallizes in a trigonal modification, a = 5.717 ± .003 Å, c = 4.667 ± .003 Å . Pure palladium difluoride has been produced in two reactions. These reactions are: (1) the thermal decomposition of fluoselenonium hexafluopalladate (IV), and (2) the reduction of palladium trifluoride with selenium tetrafluoride. The magnetic moment of the bromine trifluoride adduct of palladium trifluoride has been measured and found to be 2.2 B.M. Evidence is presented for the existence of a potassium salt of the trifluopalladate (II) ion. It has not been possible to prepare complex fluorides of terpositive palladium in selenium tetrafluoride solution. / Science, Faculty of / Chemistry, Department of / Graduate

Palladium catalyzed reactions of derivatives of 2,4-diiodophenol are explored. Coupling reactions with a series of terminal alkynes and formylation are found to be efficient and regioselective. Coupling with stananne reagents and alkenes do not work. The nature of the oxygen protecting group is critical. The phytotoxic natural product, Eutypine, is synthesized by using regioselective formylation and alkyne coupling. An approach to the plant antimicrobial compound Plicatin B is examined.

The problem of interest in this investigation was to determine the cross sections of five nuclear reactions which occur when irradiating natural palladium with neutrons which have energy values of 15.1, 15.9, and 16.3 MeV. The cross sections were measured relative to a copper monitor which was "sandwitched" in with the palladium target.

Orientador: Mario de Jesus Mendes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T06:25:56Z (GMT). No. of bitstreams: 1 Guimaraes_PauloRobertoBritto_M.pdf: 5309423 bytes, checksum: aa92c3d0424e0c6594e206702de2cbbe (MD5) Previous issue date: 1991 / Resumo: Neste trabalho foram estudadas as modificações introduzidas nas propriedades dos catalisadores de Paládio em função do teor de 'LA' 'O IND. 3' (óxido de Lantânio) presente nos mesmos. Para tanto foram preparados catalisadores de 5% Pd/'AL IND. 2' 'O IND. 3', 5% Pd-1% 'La IND. 2' 'O IND. 3'/ 'AL IND. 2' 'O IND. 3', 5% Pd/'AL IND. 2' 'O IND. 3'-'LA IND. 2' 'O IND. 3'. O método de preparação utilizado foi o da impregnação por via seca, tendo-se usado o Pd'CL IND.2', dissolvido em HCl 1N, como precursor. Após secagem a 393 K ('120 GRAUS'C) por 12h, e calcinação a 773 K ('500 GRAUS'C) por 4h, os catalisadores foram caracterizados através dos métodos de B.E.T., T.P.R., T.P.D., Quimissorção Seletiva de 'H IND. 2', Espectroscopia de Infra-vermelho, X.P.S.(E.S.C.A.), Difração de Raios-X, e um teste de atividade, através da hidrogenação do Etileno ('C IND. 2' 'H IND. 4'). Os resultados experimentais obtidos demonstraram que um alto teor de 'LA IND. 2' 'O IND. 3' modifica significativamente os perfis de redução e de dessorção de 'H IND. 2' dos catalisadores de Paládio, além de inibir fortemente a quimissorção de CO, não afetando, porém, a quimissorção de 'H IND. 2'. Além disso, verifica-se que as dispersçoes metálicas observadas nesses catalisadores são maiores que as obtidas naqueles com pouco (1%) ou nenhum 'LA IND. 2' 'O IND. 3'. Por fim, existem evidências de que, durante o processo de calcificação, ocorre a formação de um óxido misto contendo Paládio e Lantânio / Abstract: This work intended to study the changes observed on the properties of Palladium catalysts as a function of their 'LA IND. 2' 'O IND. 3' (Lanthanum oxide) content. The study was performed through the preparation and characterization of the following four catalysts: 5% Pd/'AL IND. 2' 'O IND. 3', 5% Pd-1% 'LA IND. 2' 'O IND. 3'/ 'AL IND. 2' 'O IND. 3', 5% Pd/'AL IND. 2' 'O IND. 3'-'LA IND. 2' 'O IND. 3' and 5% Pd/'LA IND. 2' 'O IND. 3'. These catalysts were prepared by the incipient wetness impregnation method, with Pd'CL IND. 2', dissolved in a 1N HCl solution, being used as Palladium precursor. After being dried at 393 K ('120 GRAUS'C) for 12h, and calcined at 773 K ('500 GRAUS'C) for 4h, thecatalysts were characterized through the methods of B.E.T., T.P.R., T.P.D., Hydrogen Chemisorption, Infrared Spectroscopy, X.P.S.(E.S.C.A.), X-Ray Diffraction, and an activity testm through ethylene ('C IND. 2' 'H IND. 4') hydrogenation. The experimental data obtained showed that a high 'LA IND. 2' 'O IND. 3' content greatly alters the Palladium catalysts reduction and 'H IND. 2' desorption profiles, and improves Pd dispersion. Furthermore, it inhibits CO chemisorption, although it does not affect 'H IND. 2' chemisorption. Besides, these data bring evidence of the formation of a mixed oxide of Lanthanum and Palladium, during the catalyst calcinations process / Mestrado / Mestre em Engenharia Química

M.Sc. / The main objective of this study was to identify and optimise the homogeneous catalytic systems for Pd(II) catalysed alkene acetoxylation in acetic acid to directly yield allyl or vinyl acetates as opposed to the usual aldehydes or ketones. Part of the intention of this study was to investigate potentially suitable re-oxidants and reaction conditions suitable for industrial application. The synthesis of butenyl acetate (via 1-butene acetoxylation) in particular is regarded as a potential value-adding opportunity for solvents producers. For safety considerations the study was performed with liquid alkenes (cyclohexene, cyclopentene, cycloheptene, cyclooctene and 1-hexene). Cyclohexene was used for the bulk of these studies. One of the most important and pioneering reactions in this field is the similar system for the oxidation of alkenes to ketones (the Wacker process). The related reaction, oxidative acetoxylation, is the result of the discovery of the Wacker process. The problems associated with both these reactions is the difficulty in re-oxidising the catalyst Pd once it has been reduced in the catalytic process from Pd(II) to Pd(0). Various reaction systems have been developed to improve these processes. Some of the systems that have been developed in the acetoxylation of alkenes were investigated. From the studies it has become obvious that for ease of Pd(0) re-oxidation a co-catalyst, benzoquinone, is essential for the catalytic process. This system employing a co-catalyst required another oxygen efficient re-oxidant to oxidize hydroquinone once reduced from benzoquinone in the oxidation of Pd(0). The re-oxidant would in turn be oxidized by oxygen. Various types of re-oxidants such as Cu(II) salts, heteropolyacids and metal macrocycles (e.g. Schiff base complexes and phthalocyanine metal complexes) were investigated in the multi-step electron transfer process. The most promising of the systems was the Pd(OAc)2/ benzoquinone/ heteropolyacid (H5PMo10V2O40 .34H2O)/ O2 system. From the studies it was apparent that the type of the re-oxidant can influence the yield of the product. Various other parameters were found to influence the reaction outcome. The type of Pd(II) salt was found to be influential in the reaction, for instance Pd(OAc)2 was found to be a better catalyst than Pd(CF3CO2)2. The catalyst loading was found to improve the yield iv when increased whilst this was not trivial since Pd is expensive the system needed to have as low catalyst loading as possible. The type of alkene used dictated the rate of the reaction and the product distribution. It was found that the conditions used for cyclohexene were not transferable to other alkenes without changing certain parameters to suit the alkene in question. Cycloalkenes acetoxylation was found to proceed without the addition of the strong nucleophile additive NaOAc, whilst for 1-hexene acetoxylation the reaction did not proceed without the additive. The product distribution was found to also differ between cycloalkenes and 1-hexene. For cyclohexene the by-products observed were the disproportionation products cyclohexane and benzene. In the case of 1-hexene the by-products were 2-hexanone (the Wacker reaction) and 2-hexenes (isomerisation). The operating temperature also played a role in the reaction outcome. In some instances the increase in reaction temperature negatively affected the reaction whilst in other cases it improved the reaction. Oxygen pressure also influenced the reaction to a lesser extent, with an increase in pressure favouring the reaction.

The adsorption and separation of Pd(II) from Pt(IV), Ir(IV) and Rh(III) by silica microparticles functionalized with triethylenetetramine (TETA), 2-(2-aminoethylthio)ethanamine (NSN) and 2-(2-(2-aminoethyl)ethylthio)ethanamine (NSSN) in 1 M hydrochloric acid medium was investigated by continuous column studies. The functionalized sorbent materials were characterized by microanalysis, SEM-EDS and FT-IR. Palladium selectivity of the sorbent materials was achieved by stripping of rhodium, iridium and platinum chlorido species with 0.5 M of NaClO4 in 1 M HCl while [PdCl4]2 was eluted with 3% w/v thiourea. The desorption efficiency of thiourea was confirmed by the SEM-EDS analysis of the materials after Pd(II) elution. Palladium loading capacity of the sorbents were in the order S-NSSN (23.85 mg/g) > S-NSN (12.70 mg/g) > S-TETA (4.97 mg/g). The extraction patterns on the sorbent materials were explained by considering the coordination chemistry of the ligand with [PdCl4]2ˉ and ionic interactions of [PtCl6]2ˉ and [IrCl5(H2O]ˉ. The square planar complexes, [Pd(HNSSNH)Cl2]Cl2 and [Pd(NSNH)Cl2][PdCl4]2, were isolated, analyzed by spectroscopy and single crystal X-ray, whereas evidence of the fraction of Pd(II)-TETA complex was obtained by HPLC studies. This provided proof of the inner sphere coordination mechanism as the mode of interaction of these ligands with [PdCl4]2ˉ. Trace amounts of Brˉ anions in ligands resulted in the inadvertent isolation of bromide coordinated Pd(II) NSN and NSSN complexes. The ion-pair salts of [TETAH4]4+ with [PtCl6]2ˉ, [IrCl6]3ˉ and [RhCl6]3ˉ were also isolated and characterized by microanalysis and IR to further explain the extraction patterns.