Dissertations / Theses: 'Palladium/platinum compounds'

1

Burrows, Andrew David. "Cluster compounds of palladium and platinum." Thesis, University of Oxford, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302903.

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Hoogervorst, Wilhelmus Johannes. "Isophthalaldimine compounds of palladium, platinum and rhodium." [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2003. http://dare.uva.nl/document/69284.

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3

Ezomo, O. J. "Studies on palladium and platinum cluster compounds." Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.234990.

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4

Chiffey, Andrew Francis. "Bimetallic compounds of palladium, platinum and gold." Thesis, University of Southampton, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.294602.

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5

Kelly, P. F. "Sulphur-nitrogen compounds of platinum and palladium." Thesis, Imperial College London, 1987. http://hdl.handle.net/10044/1/46826.

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6

Tarlton, Stephen Vijay. "Low oxidation state compounds of palladium and platinum." Thesis, Imperial College London, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.300855.

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7

Louw, Marissa. "New platinum and palladium complexes: their anticancer application." Thesis, Nelson Mandela Metropolitan University, 2010. http://hdl.handle.net/10948/d1016218.

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Novel non-leaving groups were employed in this dissertation to synthesize platinum complexes which can assist in the understanding or improvement of anticancer action. Emphasis was placed on (NS)-chelate and (NN)-chelate platinum complexes. Bidentate (NS)-donor ligands were used as non-leaving ligands in the synthesis of platinum(II) complexes with iodo, chloro, bromo and oxalato groups as leaving groups. These complexes were synthesized and studied since many questions regarding the interaction of sulfur-donors and platinum still exist. These relate to thermodynamic and kinetic factors and their influence on anticancer action. In this dissertation the properties of novel platinum(II) complexes of a bidentate ligand having an aromatic nitrogen-donor atom in combination with a thioethereal sulfur atom capable of forming a five-membered ring with platinum(II) were studied. The general structure of the (NS)-ligands used was 2-((alkylthio)methyl)pyridine. Alkyl groups used were methyl, ethyl, propyl, benzyl and phenyl. Amine complexes of platinum have been studied extensively in the past. However, attention was given to novel aspects of substituted pyridine and imidazole ligands and their corresponding complexes. Amongst these are 2-(2-methylaminoethyl)pyridine, 1-methyl-2-methylaminoethylimidazole and 1-methyl-2-methylaminobenzylimidazole. The leaving groups included chloro, bromo and oxalato. Mononitroplatinum(IV) complexes were prepared using novel synthetic methods. Selected platinum(II) amine complexes were used as starting materials for this synthesis. Some of these compounds exhibit promising anticancer behaviour. (Trans-(R,R)-1,2-diaminocyclohexane)(oxalato)(mononitrochloro)platinum(IV) is a particularly good anticancer agent and has been patented internationally. All these complexes were characterized using mass spectrometry, chromatography, thermogravimetric analysis, kinetic aspects such as ligand exchange rates and finally their anticancer action against three different cancer cell lines was evaluated via cytotoxicity assays. Some of the compounds exhibited particularly good anticancer potential.

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8

Hill, Christopher M. "The synthesis of novel cluster compounds of palladium and platinum." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334864.

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9

曾炳堯 and Biing-chiau Tzeng. "Design, structures, spectroscopic, and photophysical properties of supramoleculsar gold(I), platinum(II), and palladium(II) complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1998. http://hub.hku.hk/bib/B31237782.

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Tzeng, Biing-chiau. "Design, structures, spectroscopic, and photophysical properties of supramoleculsar gold(I), platinum(II), and palladium(II) complexes /." Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19471397.

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11

Tao, Chi-hang, and 陶志恆. "Synthesis and luminescence studies of branched carbonrich platinum(II)and palladium(II) alkynyl complexes: versatile building blocks for multinuclear assemblies." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2004. http://hub.hku.hk/bib/B31246011.

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12

Chow, Pui-keong, and 周沛強. "Luminescent palladium(II) and platinum(II) complexes with tridentate monoanionic and tetradentate dianionic cyclometallated ligands : structures, photophysical properties and material application." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2013. http://hdl.handle.net/10722/193416.

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Four structural isomers of platinum(II) complexes with C-deprotonated R-C^N^N-R’ cyclometallated ligands (R-C^N^N-R’ = -extended 6-aryl-2,2’-bipyridine derivatives containing 2-naphthyl, 3-isoquinolinyl, 1-isoquinolinyl or 2-quinolinyl moieties) have been synthesized with their photophysical properties investigated. The one bearing a 3-isoquinolinyl moiety shows the highest emission quantum yield among the four and hence has been extensively modified to give a series of complexes with different ancillary ligands (chloride, iodide, phenoxide, or acetylide). Most of these complexes show vibronic emission (max = 515–644 nm) with high emission quantum yield (up to unity) in degassed CH2Cl2; one of them has been used for OLED fabrication and shows a maximum EQE of 8.15 % with current efficiency of 25 cd A–1. The photocatalytic properties of these derivative complexes for oxidative tertiary amine functionalization have also been examined. Several highly robust and emissive platinum(II) complexes supported by two types of tetradentate O^N^C^N ligand systems (Φem up to 0.99; Td up to 520 ℃) have been synthesized and show different emission energies (λmax = 482–561 nm). Most of them exhibit excimeric emission in solution state at room temperature which are dependent on the modifications on the tetradentate O^N^C^N ligands. DFT/TDDFT calculations reveal that the metal complex showing the most intense excimeric emission possesses an excimeric excited state with a localized structure, which is unusual for these classes of platinum(II) complexes. Based on this finding, WOLED (ηL(max) = 71.0 cd/A, ηp(max) = 55.8 lm/W, ηExt = 16.5 %, CIE = 0.33, 0.42, CRI = 77) and WPLED (ηL(max) = 17.0 cd/A, ηp(max) = 9.1 lm/W, ηExt = 9.7 %, CIE = 0.43, 0.45, CRI = 78) based on this complex have been fabricated with high efficiency achieved. Palladium(II) complexes containing C-deprotonated R-C^N^N-R’ cyclometallated and pentafluorophenylacetylide ligands exhibit phosphorescence in both solid state and fluid solutions at room temperature with some of them exhibiting aggregation-induced emission (AIE). These complexes have been applied as photosensitizers in light-induced oxidative functionalization of secondary and tertiary benzylic amines as well as in light-induced hydrogen production, with a maximum of 175 turnovers for hydrogen produced. Palladium(II) complexes containing two types of tetradentate dianionic O^N^C^N ligand systems (Systems 1 and 2) have been prepared and show constrasting photophyical properties. A full scale time-resolved spectroscopic analysis has been done on some of these complexes and a platinum(II) analogue. These complexes are found to have similar excited state decay pathway( 〖S_1〗^i→〖S_1〗^f→T) with ΦISC of about unity. The emission efficiency of System 2 complexes is superior to that of System 1 complexes, which is ascribed to the suppression of excited state distortion on the basis of the results of DFT calculations. A lower radiative decay rate of System 2 palladium(II) complexes relative to the platinum(II) analogue has been found, which could be due to their lower spin-orbit coupling constant. One of the palladium(II) complexes has been applied in vacuum-deposited OLEDs with maximum current density, power efficiency and EQE of 20.0 cd A^(-1), 13.6 lm W^(-1) and 7.4 % respectively. In addition, applications of these palladium(II) complexes as photosensitizers for oxidation of secondary amines have been examined.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy

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13

Smythe, Nicole. "Reactivity studies of platinum(IV) hydroxide and methoxide complexes and the study of pincer palladium(II) complexes as potential catalysts for olefin epoxidation /." Thesis, Connect to this title online; UW restricted, 2004. http://hdl.handle.net/1773/8618.

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14

Daghriri, Hassan. "Studies on Tumour Active Compounds with Multiple Metal Centres." University of Sydney. Biomedical Sciences, 2004. http://hdl.handle.net/2123/595.

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Four tumour active trinuclear complexes: DH4Cl: [{trans-PtCl(NH3)2}2m-{trans-Pd( NH3)2(H2N(CH2)4NH2)2]Cl4, DH5Cl: [{trans-PtCl(NH3)2}2m-{trans-Pd( NH3)2(H2N(CH2)5NH2)2]Cl4, DH6Cl: [{trans-PtCl(NH3)2}2m-{trans-Pd( NH3)2(H2N(CH2)6NH2)2]Cl4, DH7Cl: [{trans-PtCl(NH3)2}2m-{trans-Pd(NH3)2-( H2N(CH2)7NH2)2]Cl4 and one dinuclear complex DHD: [{trans-PtCl(NH3)2}�-{ H2N(CH2)6NH2}{trans-PdCl(NH3)2]Cl(NO3), have been prepared and characterised based on elemental analyses, IR, Raman, mass and 1 H NMR spectral measurements. For the trinuclear complexes, the synthesis has been carried out using a step-up method branching out from the central palladium unit. A purity of about 95% has been obtained by repeated dissolution and precipitation. The activity against human cancer cell lines including ovary cell lines: A2780, A2780 cisR , A2780 ZD0473R , non small lung cell line: NCI-H640 and melanoma: Me-10538 have been determined based on MMT assay. Cell uptakes, DNA-binding have been determined for ovary cell lines: A2780, A2780 cisR . The nature of interaction with pBR322 plasmid DNA and ssDNA has been studied for trinuclear complexes DH4Cl, DH5Cl, DH6Cl and DH7Cl and the dinuclear complex DHD. Interaction of DH6Cl with adenine and guanine has also been studied by HPLC. The compounds are found to exhibit significant anticancer activity against cancer cell lines especially ovarian cancer cell lines: A2780, A2780 cisR and A2780 ZD0473R . DH6Cl in which the linking diamine has six carbon atoms is found to be the most active compound. As the number of carbon atoms in thelinking diamine is changed from the optimum value of six, the activity is found to decrease, illustrating the structure-activity relationship. The increase in uptake of the trinuclear complexes in A2780 cell line with the increase in size of the linking diamine coupled with the low molar conductivity values found for the solutions of the compounds suggest that the compounds would remain in solution as undissociated �molecules� and hence could cross the cell membrane by passive diffusion. Much lower resistance factors for the all the multinuclear compounds including DHD as applied to A2780 cisR cell line, as compared to that for cisplatin, suggest that the compounds are able to overcome multiple mechanisms of resistance operating in the cell line. All of the multinuclear complexes are expected to form long-range interstrand GG adducts with DNA, causing irreversible global changes in the DNA conformation but unlike cisplatin do not cause sufficient DNA bending to be recognized by HMG 1 protein. Increasing prevention of BamH1 digestion with the increase in concentration of the multinuclear compounds also provide support to the idea that the compounds because of the formation of a plethora of interstrand GG adducts are able to cause irreversible changes in DNA conformation. The results of the study show that indeed new trinuclear tumour active compounds can be found by replacing the central platinum unit in BBR3464 with other suitable metal units.

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15

Hung, Faan-fung, and 孔繁峰. "Luminescent platinum(II), palladium(II) and gold(III) complexes containing isocyanide, alkynyl and N-heterocyclic carbene ligands : synthesis, photophysical properties and material applications." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2014. http://hdl.handle.net/10722/206318.

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16

蔡子良 and Chi-leung Dickson Choi. "Vibrational reorganization energies of the LMCT transition of PdCI2(PPh3)2 and the MLCT transition of several Pt-acetylide complexesdetermined by resonance Raman intensity analysis." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1998. http://hub.hku.hk/bib/B31215154.

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17

Choi, Chi-leung Dickson. "Vibrational reorganization energies of the LMCT transition of PdCI2(PPh3)2 and the MLCT transition of several Pt-acetylide complexes determined by resonance Raman intensity analysis /." Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19945814.

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18

Thu, Hung-yat. "Catalytic C-H bond functionalization reactions catalyzed by rhodium(III) porphyrin, palladium(II) and platinum(II) acetate complexes." View the Table of Contents & Abstract, 2006. http://sunzi.lib.hku.hk/hkuto/record/B38027872.

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19

Deetlefs, Maggel. "Carbene and coordination complexes of gold, palladium, platinum and manganese derived from N-containing heterocycles." Thesis, Stellenbosch : Stellenbosch University, 2001. http://hdl.handle.net/10019.1/52155.

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20

Thu, Hung-yat, and 杜鴻溢. "Catalytic C-H bond functionalization reactions catalyzed by rhodium(III) porphyrin, palladium(II) and platinum(II) acetatecomplexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B38798268.

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21

Gerdin, Martin. "Silaborations of Unsaturated Compounds." Doctoral thesis, Stockholm : Chemical Science and Engineering, Kungliga Tekniska högskolan (KTH), 2008. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-9440.

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22

Ferrandon, Magali. "Mixed metal oxide - noble metal catalysts for total oxidation of volatile organic compounds and carbon monoxide." Doctoral thesis, Stockholm, 2001. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3156.

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23

Costa, Marinez Maciel da. "Síntese e caracterização de compostos de coordenação contendo Pd(II), Pt(II) e ligantes do tipo oxamato." Universidade Federal de Juiz de Fora (UFJF), 2009. https://repositorio.ufjf.br/jspui/handle/ufjf/4414.

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CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Neste trabalho são descritas a síntese e caracterização de oito precursores inéditos, dois contendo Pt2+ e seis contendo Pd2+, além de ligantes do tipo oxamato. São eles: [Pt(opba)].H2O, [Pt2(ppba)2].H2O, K2[Pd(opba)].H2O, K2[Pd{Pd(opba)}(H2O)2].H2O, [Pd(mpba)].2H2O, K2[Pd(mpba)].2H2O, [Pd2(ppba)2].4H2O e K4[Pd2(ppba)2].4H2O. Os precursores foram obtidos a partir da reação entre ligantes oxamato, em sua forma de ácido ou éster, e o sal do íon metálico divalente correspondente, em solução aquosa. Os ligantes, ácidos N,N’-1,2-fenilenobis(oxâmico) (H4opba), ácido N,N’-1,3-fenilenobis(oxâmico) (H4mpba) e ácido N,N’-1,4-fenilenobis(oxâmico) (H4ppba), foram obtidos a partir dos respectivos ésteres, N,N’-1,2-fenilenobis(oxamato) de etila (opba), N,N’-1,3-fenilenobis(oxamato) de etila (mpba) e N,N’-1,4-fenilenobis(oxamato) de etila (ppba), conforme descrito na literatura. Os magnetos moleculares trinucleares inéditos, [Pd(opba){Cu(bpca)}2].3DMSO. H2O e [Pd(ppba)2{Cu(bpca)}2].5DMSO.5H2O, foram obtidos a partir da reação entre os precursores K2[Pd(opba)].H2O e [Pd2(ppba)2].4H2O e [Cu(bpca)(H2O)2]NO3.2H2O, onde bpca= bis(2-piridilcarbonil)amidato. As propriedades magnéticas foram investigadas na forma das curvas de ᵡT versus T e M versus H. Os resultados indicaram que ambos os compostos possuem interações antiferromagnéticas a baixas temperaturas, e ainda sugerem que o íon Pd2+ em [Pd(ppba)2{Cu(bpca)}2].5H2O.5DMSO apresente geometria octaédrica. Todos os compostos obtidos neste trabalho foram caracterizados por análise elementar, espectroscopia vibracional na região do IV. Os ligantes e os precursores também foram caracterizados por ressonância magnética nuclear de carbono (RMN-13C) e hidrogênio (RMN-1H). Para a determinação do número de moléculas de solvente, foi utilizada a análise térmica.
In this work the synthesis and characterization of eight new precursors are described, two containing Pt2+ and six containing Pd2+, in addition to the synthesis of oxamatotype ligands. The precursors are: [Pt(opba)].H2O, [Pt2(ppba)2].H2O, K2[Pd(opba)].H2O, K2[Pd{Pd(opba)}(H2O)2].H2O, [Pd(mpba)].2H2O, K2[Pd(mpba)].2H2O, [Pd2(ppba)2].4H2O and K4[Pd2(ppba)2].4H2O. They were obtained by reaction of the oxamato ligands, in their acid or ester form, with the correspondent divalent metallic ion salt, in aqueous solution. The acid ligands, namely N,N’-1,2-phenylenebis(oxamic) acid (H4opba), N,N’-1,3-phenylenebis(oxamic) (H4mpba) and N,N’-1,4-phenylenebis(oxamic) acid (H4ppba) were obtained from their respective esters, N,N’-1,2-phenylenebis(oxamato) ethyl ester (opba), N,N’-1,3-phenylenebis(oxamato) ethyl ester (mpba) and N,N’-1,4-phenylenebis(oxamato) ethyl ester (ppba), according to procedures described in the literature. Trinuclear molecule-based magnets, [Pd(opba){Cu(bpca)}2].3DMSO.H2O and [Pd(ppba)2{Cu(bpca)}].5DMSO.5H2O were obtained by reaction of the K2[Pd(opba)].H2O and [Pd2(ppba)2].4H2O precursors with [Cu(bpca)(H2O)2]NO3.2H2O, where bpca= bis(2-pyridylcarbonyl)amine. The magnetic properties were investigated by the ᵡT versus T and M versus H plots. The results indicate that both compounds show antiferromagnetic interactions at low temperatures, and also suggest that the Pd2+ ion in the [Pd(ppba)2{Cu(bpca)}2].5DMSO.5H2O compound presents an unexpected octahedral geometry. All compounds obtained in this work were characterized by elemental analysis and vibrational spectroscopy (IR). Ligands and precursors were also characterized by carbon and hydrogen nuclear magnetic resonance (13C NMR and 1H NMR). Thermal analysis was used to determine the number of solvent molecules.

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YOVANOVICH, MARCOS. "Oxidação eletroquímica do ácido fórmico em eletrólito ácido e básico utilizando eletrocatalisadores PtBi/C e PdBi/C preparados pelo método de redução via borohidreto de sódio adição rápida." reponame:Repositório Institucional do IPEN, 2016. http://repositorio.ipen.br:8080/xmlui/handle/123456789/26799.

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PtBi/C e PdBi/C foram preparados em diferentes razões atômicas (100:0, 90:10, 80:20, 70:30, 60:40 e 50:50) pelo método de redução via borohidreto de sódio (com adição total da solução de borohidreto em uma única etapa) utilizando H2PtCl6.6H2O, Pd(NO3)2, (BiNO3)3.5H2O como fonte de metais, Vulcan® (XC72-Cabot) como suporte de carbono e com uma carga metálica correspondente a 20% em massa. Os eletrocatalisadores obtidos foram caracterizados por difração de raios-X (DRX), microscopia eletrônica de transmissão (MET) e voltametria cíclica (VC). A atividade dos diferentes materiais preparados para a oxidação eletroquímica do ácido fórmico foi realizada em eletrólito ácido e alcalino utilizando-se as técnicas de voltametria cíclica, e cronoamperometria. Para estes estudos foi utilizado a técnica do eletrodo de camada fina porosa. A caracterização eletroquímica permitiu comparar o desempenho eletroquímico da platina e paládio, além de avaliar o benefício da presença do bismuto nas razões atômicas propostas. Os difratogramas de raio-X (DRX) confirmaram para todos os compostos de PtBi/C e PdBi/C a formação da estrutura cúbica de face centrada (cfc) característicos da rede cristalina da platina e do Paládio respectivamente. Outros picos encontrados foram associados a presença de fases de óxido de bismuto em ambos os compostos, PtBi/C e PdBi/C. A microscopia eletrônica de transmissão (MET) indicou que a presença de maiores teores de bismuto não acarretaram em aumento do tamanho médio da partícula. Os resultados eletroquímicos em meio alcalino indicaram que ainda é necessário uma otimização da concentração de ácido fórmico para que possamos observar melhores resultados quanto à adição de bismuto na platina ou paládio, no entanto os estudos em meio ácido mostraram o efeito benéfico da adição de bismuto tanto para platina quanto para o paládio.
Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Cadieu, Marie-Claude. "Reactions de contact des octanes sur des catalyseurs a base de platine et de palladium." Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13023.

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Etude des differences de comportements catalytiques entre des catalyseurs supportes pt et pd a partir d'un nouveau type d'hydrocarbure test: les octanes. Mecanisme de cyclisation et d'isomerisation des aliphatiques et d'hydrogenolyse des cyclopentanes

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26

Agbossou, Sénamé. "Ligands aminophosphonites et complexes de metaux des groupes 9 et 10 : syntheses et applications en oligomerisation, telomerisation et carbonatation." Toulouse 3, 1988. http://www.theses.fr/1988TOU30110.

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Preparation et caracterisation d'une serie de comples de palladium, de platine et de rhodium renfermant les ligands dioxa-1,3-phospha-2-aza-6 r-6 phenyl-2-cyclooctane (r=h,phn; r=me,pnme; r=methyl-2allyle, pnallyle)

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27

Soules, Régis. "Proprietes cooperatives de complexes polymetalliques des ligands squarate et thiosquarate." Toulouse 3, 1987. http://www.theses.fr/1987TOU30178.

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Etude de l'emploi d'un coordinat assembleur qui puisse par coordination avec le centre metallique utilise (metaux de transition du groupe viii) aboutir a un agencement a une dimension des motifs moleculaires par empilement d'entites monomeres ou par formation de chaines. Par utilisation du coordinat squarate sous ses formes oxygenees et soufrees, obtention d'un certain nombre de complexes de pt, pd, ni et cu repondant aux criteres fixes. Etude des structures de ces composes, de leurs proprietes physiques et de la relation structure-propriete. La nature du coordinat comme le caractere specifique de l'arrangement structural ont ete discutes pour une approche de la comprehension de la nature de ces proprietes physiques

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Colineau, Eric. "Etude des propriétés magnétiques et électroniques de composés de neptunium NpX3 et Np2T2X par spectroscopie Mossbauer, diffraction de neutrons et magnétométrie SQUID." Université Joseph Fourier (Grenoble), 1996. http://www.theses.fr/1996GRE10107.

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Le travail presente dans cette these est une contribution a l'etude des proprietes magnetiques et electroniques des composes intermetalliques npx#3 (x=al, ga, in, sn) et np#2t#2x (t=co, ni, ru, rh, pd, pt ; x=in, sn) par spectroscopie mossbauer, diffraction de neutrons et magnetometrie squid. L'interet de ces series est de presenter une hybridation progressive des electrons 5f du neptunium avec les orbitales des ligands et une reduction concomitante du magnetisme lorsque le numero atomique des elements x ou t diminue. Il est donc possible d'observer, le long d'une meme serie isostructurale, l'evolution des proprietes magnetiques et electroniques, de l'ordre magnetique avec des electrons 5f localises, jusqu'au paramagnetisme de pauli avec des electrons 5f totalement delocalises. Pour chaque famille de composes etudies, est etablie une comparaison avec les familles homologues ou le neptunium est remplace par l'uranium ou le cerium. La serie npx#3 a fait l'objet d'un certain nombre d'etudes depuis une vingtaine d'annees, et les resultats presentes ici completent et precisent les connaissances anterieures de ces composes. Les diagrammes de phases et les structures magnetiques de npal#3, npga#3 et npin#3 ont ete completes et precises. Le facteur de forme et la carte de densite d'aimantation de npsn#3 ont ete mesures. L'etat de charge et l'etat fondamental du neptunium dans ces composes sont discutes. La serie np#2t#2x a ete recemment decouverte et les resultats exposes dans ce memoire constituent la premiere etude des proprietes magnetiques et electroniques de ces composes. Les mesures de spectrometrie mossbauer ont permis d'etablir que huit de ces composes s'ordonnent et trois ne s'ordonnent pas. Nous avons determine les temperatures de mise en ordre, la valeur du moment a saturation porte par le neptunium et l'etat de charge du neptunium

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29

Takky, Driss. "Effet de la structure moléculaire en electrocatalyse : étude mécanistique de l'oxydation des isomères du butanol en milieu aqueux sur diverses électrodes de metaux nobles." Poitiers, 1987. http://www.theses.fr/1987POIT2008.

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30

Nemra, Ghinwa. "Comportement electrochimique de nouveaux complexes a liaison pd-pd et pt-pd stabilises par des ligands bidentates ph : :(2)pch::(2)pph::(2)." Strasbourg 1, 1986. http://www.theses.fr/1986STR13055.

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Abstract:

L'etude des proprietes redox d'une vingtaine de complexes mono-, di-, tri- et tetranucleaires du palladium et du platine a ete effectuee par des methodes electrochimiques (electrode a disque tournant, voltamperometrie cyclique et coulometrie) associees a des methodes spectroscopiques (spectrophotometrie d'absorption electronique, rpe et rmn). Les differents mecanismes des reactions redox ont ete etablis en fonction de la nature des metaux et des ligands dans le complexe. On montre qu'on peut modifier de maniere controlee les potentiels d'oxydoreduction et la reversibilite des transferts de charge par un choix convenable de parametres: metaux, ligands (phosphine, co) et milieu d'etude. Les resultats obtenus contribuent a l'etude de la reactivite electrochimique de la liaison metal-metal dans les complexes des metaux de transition

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31

Faulmann, Christophe. "Conducteurs derives de metaux de transition : complexes moleculaires, polymeres, oxydes de cuivre." Toulouse 3, 1988. http://www.theses.fr/1988TOU30160.

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32

Keter, Frankline Kiplangat. "Palladium, platinum and gold complexes: a synthetic approach towards the discovery of anticancer agents." Thesis, 2010. http://hdl.handle.net/10210/3074.

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Ph.D.
Ligands bis(pyrazolyl)acetic acid (L1) and bis(3,5-dimethylpyrazolyl)acetic acid (L2) were synthesised by reacting pyrazoles and dibromoacetic acid under phase transfer conditions, by using benzyltriethylammonium chloride as the catalyst. Ligands L1 and L2 were characterised by a combination of 1H, 13C{1H} NMR, IR spectroscopy and microanalysis. Esterification of L1 and L2 led to formation of bis(pyrazolyl)ethyl acetate (L3) and bis(3,5-dimethylpyrazolyl)ethyl acetate (L4). Ligands L3 and L4 were also characterised by a combination of 1H, 13C{1H} NMR, IR spectroscopy and microanalysis. Subsequently, new pyrazolyl palladium(II) and platinum(II) compounds, [PdCl2(L1)] (1), [PdCl2(L2)] (2), [PtCl2(L1)] (3a) and [PtCl2(L2)] (4) were prepared by reacting bis(pyrazolyl)acetic acid ligands (L1-L2) with K2[PdCl4] or K2[PtCl4] respectively. The structures of complex 1 and 2 reveal distorted square planar geometries. The bond angles of N-Pd-N, N-Pd-Cl, N-Pd-Cl, for 1 and 2 are between 85.8(3)o and 90.81(4)o). The platinum compound, K2[Pt4Cl8(L1)2(deprotonated-L1)2].2H2O (3b), crystallised from aqueous solutions containing 3a when such solutions were left to stand overnight. Each platinum coordination environment consists of two cis-Cl ligands and one K2-N^N(L1) unit (L1 = bis(pyrazolyl)acetic acid), with two ligand moieties in 3b that are deprotonated with two K+ counter ions. Reaction of bis(pyrazolyl)acetic acid ligands (L1-L2) with [HAuCl4].4H2O gave gold(III) complexes [AuCl2(L1)]Cl (5a) and [AuCl2(L2)]Cl (6a). The spectroscopic, mass spectroscopy and microanalysis data were used to confirm the formation of the desired complexes. However, attempts to crystallise 5a and 6a led to formation of [AuCl2(pz)(pzH)] (5b) and [AuCl2(3,5-Me2pz)(3,5-Me2pzH)] (6b). This was confirmed by the structural characterisation of 5b, which has a distorted square-planar geometry. When complexes 1-6a were screened for their anti-tumour activity against CHO-22 cells, they showed no appreciable biological activities against CHO-22 cells. Substitution reactions of complexes 1-6a with L-cysteine performed to probe any relationship between the observed antitumour activities and the rates of ligand substitution of these complexes were inconclusive. Dithiocarbamate ligands L5-L8 were synthesised as potassium salts by introducing a CS2 group in positions 1 of pyrazole, 3,5-dimethylpyrazole, indazole and imidazole. The reaction of L5-L8 with [AuCl(PPh3)], [Au2Cl2(dppe)], [Au2Cl2(dppp)] and [Au2Cl2(dpph)], led to isolation of complexes [Au(L)(PPh3)] (13-16), [Au2(L)2(dppe)] (17a-19), [Au2(L)2(dppp)] (20-22) and [Au2(L)2(dpph)] (23-25) (dppe = bis(diphenylphosphino)ethane, dppp = bis(diphenylphosphino)propane, dpph = bis(diphenylphosphino)hexane; L = anions of L5-L8). The mononuclear molecular structure of 15 features a near linear geometry with a P(1)-Au(1)-S(1) angle of 175.36(2) o. The binuclear gold(I) complexes 20-22 and 23-25 have two P-Au-S moieties as evident in the solid state structure of 25. Attempts to crystallise complex 17a led to the formation of a gold(I) cluster complex [Au18S8(dppe)6]2+ (17b) as confirmed by X-ray crystallography. Cluster 17b features weak Au···Au interactions (2.9263(7)-3.1395(7) Å). Complexes 13-16 and 20-25 were tested in vitro for anticancer activity on HeLa cells. The activities of gold(I) complexes 13-16 were comparable to that of cisplatin. Dinuclear gold(I) complexes 20-25 also showed appreciable antitumour activity against HeLa cells. However, the dpph gold(I) compounds (23-25) were highly active, with 24 showing the highest activity against HeLa cells (IC50 = 0.1 μM). The tumour specificity (TS) factors for 23 and 24 were 31.0 and 70.5, respectively.

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33

Tiba, Felicia. "Synthesis and kinetic studies of Pd(II), Pt(II) and Ru(II) polypyridine monoaqua complexes." Thesis, 2003. http://hdl.handle.net/10413/3248.

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The thesis is divided into three parts. The first part looks at the reactivity difference between [Pt(terpy)(OH2)f+ and [Pt(bpma)(OH2)]2+ where terpy is 2,2' :6',2"-terpyridine and bpma is bis(2-pyridylmethyl)amine, towards thiols namely, L-cysteine, DLpenicillamine and glutathione. This is followed by a comparative study of [Pt(bpma)(OH2)]2+ and [pd(bpma)(OH2)f+. Finally the reactivity differences between [Ru(terpy)(bipy)(OH2)f+ and [Ru(terpy)(tmenXOH2)]2+ are reported. Included are the synthesis and characterization ofthe complexes. The substitution behaviour of [pt(terpy)(OH2)]2+and [Pt(bpma)(OH2)f+ was studied as a function of entering thiol concentration and temperature. The reactions between the Ptcomplexes and DL-penicillamine, L-cysteine and glutathione were carried out in a 0.10 mol dm03 aqueous perchloric acid medium using stopped-flow or conventional UV-Vis spectrophotometry as required. The observed pseudo-first-order rate constants for the substitution reactions are given by kobs = k2[thiol] + k 2. The k 2 term represents the reverse solvolysis reaction. This term was found to be zero for Ptn(terpy) which was the most reactive complex. The second-order rate constants, ka; for the three thiols varied between 0.107±0.001 M·l S·l and 0.517±0.025 M"l sol for PtlI(bpma) and 10.7±0.7 M"l S·l to 711.9±18.3 M"l S·l for PtlI(terpy), with glutathione being the strongest nucleophile. Analysis of the activation parameters, Mf' and .1.S", clearly shows that the substitution process is associative in nature. The second study has looked at the substitution of the coordinated water molecule from [Pt(bpma)(OH2)f+ and [pd(bpma)(OH2)f+ by a series of nucleophiles [Nu] viz. TU, DMTU, TMTU and as well as Be", Cl', SCN", and r for the Ptn(bpma) complex. The investigation was conducted under pseudo-first-order conditions as a function of concentration of [Nu] as well as temperature for PtlI(bpma) complex using stopped flow spectrophotometry. Reactions involving PdII(bpma) were done at 10°C. The observed pseudo-first-order rate constants obeyed the equation kobs= k2[Nu]. The second-order rate constants, kz, at 10 "C for the sulfur donor nucleophiles have been found to vary between 70.35 M I sol and 223.06 M I sol for PtII(bpma) and (1.24 ± 0.01) x 105 M I sol to (2.17 ± 0.02) x 105 M-Is-l for PdII(terpy), with DMTV being the strongest nucleophile. The second-order rate constant, ka; at 25 "C fur PtII(terpy) was found to increase in the following order cr < Be" < TMfU < SCN < TV < DMTV < f. This order is in agreement with the polarizability of the nucleophiles, the nucleophilic discrimination factor being 0.38. The temperature studies for PtII(bpma) suggest that the substitution process is associative in nature.n The third part looked at the reactivities of [Ru(terpy)(bipy)(OHz)]z+ and [Ru(terpy)(tmen)(OHz)]z+ where bipy is 2,2'-bipyridine and tmen is N,N,N ',N 'tetramethylethylenediamine with three nucleophiles TV, DMTV and CH3CN. The pKa values for the complexes were found to be 9.99 and 10.27 for [Ru(terpy)(bipy)(OHz)]z+ and [Ru(terpy)(tmen)(OHz)f+, respectively. The substitution of water involving the two complexes was studied under pseudo-first order conditions using UV-Visible Spectrophotometry. The pseudo-first-order rate constant fitted the simple rate law kobs = kz [Nu] + k-z. The k.z term was found to be zero for [Ru(terpy)(bipy)(OHz)f+ but nonzero for [Ru(terpy)(tmen)(OHz)]z+. The values of the second order rate constants (kz) for the three nucleophiles were found to be between (1.08 ± 0.02) x 10-4 M l sol and (15.0 ± 0.27) x 10-4 M-l sol for [Ru(terpy)(bipy)(OHz)]z+ and (0.82 ± 0.04) x 10-4 M-l sol and (21.90 ± 0.69) x 10-4 M-I sol for [Ru(terpy)(tmen)(OHz)]z+. The results suggests that nback donation accounts for the difference in reactivity.
Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 2003.

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34

Beek, Johannus Antonius Maria van. "Synthesis and reactivity of cyclometalated Ni(II), Pd(II) and Pt(II) complexes." 1990. http://catalog.hathitrust.org/api/volumes/oclc/25889954.html.

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