Dissertations / Theses: 'Palladium compounds'

1

Farhad, Mohammad. "Studies on new trinuclear palladium compounds." Connect to full text, 2007. http://hdl.handle.net/2123/2477.

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Doctor of Philosophy(PhD)
The present study deals with the synthesis and characterization of six tri-palladium complexes code named MH3, MH4, MH5, MH6, MH7 and MH8 that contained two planaramine ligands bound to the central or each of the terminal metal ions. The activity of the compounds against human cancer cell lines: A2780, A2780cisR and A2780ZD0473R, cell uptake, levels of DNA-binding and nature of interaction with salmon sperm and pBR322 plasmid DNA have also been determined. Whereas cisplatin binds with DNA forming mainly intrastrand GG adduct that causes local bending of a DNA strand, the tri-palladium complexes are expected to bind with DNA forming a number of long-range interstrand GG adducts that would cause a global change in DNA conformation. Among the designed complexes, MH6 that has two 2-hydroxypyridine ligands bound to each of the two terminal palladium ions is found to be most active. The compound also has the highest cell uptake and Pd-DNA binding levels. In contrast, MH8 which has two 4-hydroxypyridine ligands bound to each of the two terminal palladium ions is found to be least active. The results indicate that, as applied to the terminal metal centres, 2-hydroxypyridine would be more activating than 4-hydroxypyridine perhaps because of greater protection provided to the terminal centres from coming in contact with the solvent molecules. In contrast, when bound to the central metal centre, 4-hydroxypyridine appears to play a slightly greater activating role than 2-hydroxypyridine or 3-hydroxypyridine, suggesting that non-covalent interactions such as hydrogen bonding associated with the ligand rather than its steric effect may be a more important determinant of antitumour property. The results illustrate structure-activity relationships and suggest that the tri-palladium complex containing two 2-hydroxypyridine ligands bound to each of the three metal centres or the compound that contains two 2-hydroxypyridine ligands bound to each of the two terminal metal centres and two 4-hydroxypyridine ligands bound to the central metal centre, may be much more active than any of the designed complexes.

2

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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3

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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4

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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5

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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6

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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7

Phillips, David J. "Palladium-catalysed synthesis of highly functionalised compounds." Thesis, University of Glasgow, 2018. http://theses.gla.ac.uk/9011/.

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Palladium-catalysis is extremely important in fine chemical synthesis. This thesis looks at the development of new palladium-catalysed carbon–carbon bond formation reactions, with particular attention to forming new bonds to sp3 carbons. The opening chapter of this thesis gives an overview of current methods for palladium-catalysed heterocyclisation, and the methods for incorporating further functionalisation into this process, then focuses on the optimisation and expansion of a new palladium-catalysed carboallylation reaction. The reaction mechanism was demonstrated via a deuterium-labelling study, confirming that the reaction proceeds through an isohypsic mechanism. Chapter 2 begins with a summary of palladium-catalysed isohypsic reactions, and the introduction of the isohypsic–redox sequence. New results are presented on the expansion of this isohypsic–redox sequence to include the oxyallylation–Heck-coupling, and work on the aminoallylation–Grubbs–Wacker oxidation. Chapter 3 commences with an introduction to MIDA boronates, describing their useful properties along with some uses, particularly in step-wise synthesis. The development of a new palladium-catalysed allylation of MIDA boronates is then detailed. Using MIDA boronates to form a new bond to an sp3 carbon for the first time, this was applicable to a range of allyl halides as well as a large number of MIDA boronates containing a range of functionality. Formation of a new sp3–sp3 carbon–carbon bond was explored, as well as an enantioselective allylation. The application of the allylation was demonstrated in the development of a new palladium-catalysed synthesis of Ibuprofen. Experimental procedures and data are summarised in Chapter 4. An appendix containing NMR spectra for new compounds is attached.

8

Cloete, Jezreel. "Synthesis and applications of functionalized pyridinyl imine complexes of palladium." Thesis, University of the Western Cape, 2005. http://etd.uwc.ac.za/index.php?module=etd&amp.

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The synthesis and characterization of pyridinyl &alpha
-diimine Pd(II) complexes having a functionalized hydrocarbon attached to the imino nitrogen was performed. The catalytic activity of these complexes were then evaluated in the polymerization of ethylene and in the Heck coupling reaction of methyl acrylate with iodobenzene.

Unconjugated &beta
-diimine complexes of palladium were also synthesized and their activities towards ethylene polymerization and the Heck coupling of methyl acrylate and iodobenzene also evaluated and compared to that of the &alpha
-diimine complexes. Three of the &alpha
-diimine complexes synthesized showed activity towards ethylene polymerization, these being the complexes bearing the allyl, styrene and phenol functionalities. &omega
-Carboxylato complexes which were also synthesized showed no activity towards ethylene polymerization.

The polymer produced was found to be high density linear polyethylene with an average PDI of 2.54 with Mn values ranging between 3.42 and 6.90 x 10-5 and Mw values ranging between 6.05 and 17.6 x 10-5.

The complexes bearing the allyl, styrene and phenol functionalities, as well as the &omega
-carboxylato complexes active in the Heck coupling reactions of methyl acrylate with iodobenzene. None of the unconjugated &beta
-diimine complexes prepared showed any activity towards ethylene polymerization even at high Al/Pd ratios. The activity of these complexes towards the Heck arylation reaction was comparable to that of the &alpha
-diimine complexes showing similar activities.

9

Wallner, Olov. "Palladium-Catalyzed Synthesis and Transformations of Organometallic Compounds." Doctoral thesis, Stockholm : Dept. of Organic Chemistry, Stockholm University, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-804.

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10

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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11

Zinser, Caroline Magdalene. "Palladium and gold N-heterocyclic carbene complexes : synthesis and catalytic applications." Thesis, University of St Andrews, 2019. http://hdl.handle.net/10023/17066.

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12

陳雁菁 and Suzanna Chan. "The chemistry of osmium-palladium carbonyl clusters." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1995. http://hub.hku.hk/bib/B31234628.

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13

Chan, Suzanna. "The chemistry of osmium-palladium carbonyl clusters /." Hong Kong : University of Hong Kong, 1995. http://sunzi.lib.hku.hk/hkuto/record.jsp?B18061576.

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14

Graves-Brook, Melissa Kaye. "Synthesis and characterization methods of palladium-doped ceria-zirconia compounds." Master's thesis, Mississippi State : Mississippi State University, 2005. http://sun.library.msstate.edu/ETD-db/ETD-browse/browse.

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15

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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16

Worakun, Tanachat. "Palladium and rhodium catalysed construction of carbocyclic and heterocyclic compounds." Thesis, Queen's University Belfast, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.317069.

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17

Suginome, Michinori. "Bis-silylation of Unsaturated Compounds Catalyzed by Palladium-Isocyanide Complex." Kyoto University, 1993. http://hdl.handle.net/2433/74624.

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18

Masuda, Kohei. "New Synthetic Strategy of Organosilicon Compounds Utilizing Palladium-Silylene Species." 京都大学 (Kyoto University), 2011. http://hdl.handle.net/2433/142246.

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19

Moyo, Cyprian Bertrand. "Development of Palladium selective reagents and materials." Thesis, Nelson Mandela Metropolitan University, 2016. http://hdl.handle.net/10948/12231.

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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.

20

Marelli, Enrico. "Nickel- and palladium-catalysed deprotonative cross-couplings." Thesis, University of St Andrews, 2017. http://hdl.handle.net/10023/15603.

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Transition metal-catalysed cross coupling chemistry is a valuable tool for synthetic organic chemistry, enabling the preparation of compounds of great interest. The catalytic metal of choice is usually palladium, which generally offer better performances in term of catalytic activity and easy handling. On the other hand, the use of nickel in this class of reactions is gaining attention, as it would provide more economically and environmentally sustainable processes. Deprotonative cross couplings are a subgroup of these reactions, in which the nucleophile is generated in situ by direct deprotonation of a (relatively) acidic C–H bond, for example those of an enolizable ketone or an imine. The reaction products often represent intermediates towards more complex molecular architectures, by virtue of the well-known carbonyl chemistry. The development of a Pd-catalysed methodology for the prototypical deprotonative coupling, the a-arylation of ketones, is reported in this thesis. It requires significantly lower catalyst loadings compared to previous reports, and displays good tolerance towards functionalised substrates. A related protocol for the intramolecular a-arylation of imines towards indoles was subsequently disclosed: as it requires low catalyst loadings and displays good scalability and simple setup, this methodology is a promising hit for industrial applications. The parallel development of nickel-catalysed protocols afforded an efficient method for the a-arylation of ketones, using chloroarenes as electrophile for the first time in the literature. The method was further optimised for the synthesis of an intermediate towards a commercial medicinally active compound. Building up on these findings, the first nickel-catalysed protocol for the deprotonative arylation of benzylaminederived imines was also developed. Last, the first aqueous palladium-catalysed protocol for the a-arylation of ketones was investigated. The method proved flexible, showing excellent functional group tolerance: compounds containing base-sensitive functional groups, halogenated small-molecule drugs, and Boc-protected amino acids were all suitable substrates.

21

許穎思 and Wing-sze Janesse Hui. "The chemistry of mixed-metal clusters of osmium and palladium." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1998. http://hub.hku.hk/bib/B31237095.

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22

Hui, Wing-sze Janesse. "The chemistry of mixed-metal clusters of osmium and palladium /." Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19737749.

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23

Yue, Congyong. "Palladium complexes of aromatic amide-derived phosphines and application for synthesis of biaryls, nitrogen heterocycles, and benzo[b]furans /." View abstract or full-text, 2009. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202009%20YUE.

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24

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.

25

Lo, Kai-yip, and 羅啟業. "Synthesis of aza-bicyclic compounds via palladium-catalyzed cascade cyclization reactions." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2012. http://hub.hku.hk/bib/B47849691.

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A palladium-catalyzed oxidative cascade cyclization reaction has been developed to prepare pyrrolizidine and indolizidine derivatives from simple aliphatic alkenyl amides 2.1ak in one step in moderate to good yields, using Pd(TFA)2 as the catalyst and molecular oxygen (1 atm) as a green oxidant. This cascade cyclization can also proceed for ring-containing unsaturated amides 2.1ln to afford azatricyclic systems. Palladium(II)-catalyzed dehydrohalogenation cascade cyclization reactions have been developed to synthesize polycyclic pyrrolizidine derivatives from iodoalkenylanilides 4.1ai in satisfactory to excellent yields under mild conditions. This reaction produces two stereocenters in one step and only one single diastereomer was obtained in the cyclization of 4.1. The reaction is proposed to proceed through an organopalladium(IV) species, formed by oxidative addition after the aminopalladation. This organopalladium(IV) species then undergoes reductive elimination to give the cyclized product. This cyclization is a fast and efficient way to construct natural alkaloids that contain pyrrolizidine or indolizidine cores.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy

26

Chen, Nan. "Kinetics of the hydrodechlorination reaction of chlorinated compounds on palladium catalysts." Link to electronic thesis, 2003. http://www.wpi.edu/Pubs/ETD/Available/etd-0823103-161859.

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27

Du, Wei, and 杜玮. "Palladium-catalyzed oxidative cascade cyclizations via C-N/C-C formation for synthesis of nitrogen heterocycles." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2014. http://hdl.handle.net/10722/206320.

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28

Yung, Ka-fu, and 容家富. "The chemistry of osmium-palladium mixed-metal nanoclusters and nanoparticles." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2003. http://hub.hku.hk/bib/B31245067.

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29

Champkin, Paul Anthony. "A structural and electronic study of novel palladium bis-phosphate complexes." Thesis, University of Newcastle Upon Tyne, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.391274.

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30

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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31

Shaffer, Andrew Ronald. "Synthesis, reactivity, and catalysis of 3-iminophosphine palladium complexes /." Connect to full text in OhioLINK ETD Center, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1248288981.

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Thesis (Ph. D.)--University of Toledo, 2009.
Typescript. "Submitted as partial fulfillment of the requirements for the Doctor of Philosophy in Chemistry." Includes bibliographical references (leaves 183-217).

32

Damian, Karen Serena. "Pd catalysed synthesis of phosphines for homogeneous catalysis." Thesis, St Andrews, 2009. http://hdl.handle.net/10023/907.

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33

Stürzer, Christine [Verfasser], and Dirk [Akademischer Betreuer] Johrendt. "Calcium Iron Palladium Arsenides and related compounds / Christine Stürzer. Betreuer: Dirk Johrendt." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2015. http://d-nb.info/107698102X/34.

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34

Aparece, Mark Docto. "Synthesis of Organoboron Compounds via a Palladium-Induced 1,2-Metallate Shift Mechanism:." Thesis, Boston College, 2020. http://hdl.handle.net/2345/bc-ir:108927.

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Thesis advisor: James P. Morken
This dissertation describes the development of various palladium-catalyzed syntheses of organoboron compounds with the 1,2-metallate shift of organoboron “ate” complexes as a common mechanistic feature. Chapter one discusses the history of the 1,2-metallate shift with a focus on reactions promoted by transition metals, followed by my work on the palladium-catalyzed, enantioselective, halide-tolerant conjunctive cross-coupling reaction to enable the use of Grignard reagents and arylbromides. Chapter two discusses the attempt to engage allylic electrophiles in the conjunctive cross-coupling reaction and the discovery and optimization of the vinylidenation reaction to access 1,1-disubstituted boryl alkenes. Unlike other palladium-catalyzed reactions that proceed by a 1,2-metallate shift, the vinylidenation proceeds by a β-hydride elimination rather than a reductive elimination as the final step in the catalytic cycle. Chapter three discusses the development of the enantioselective conjunctive cross-coupling of propargylic electrophiles to access enantioenriched β-boryl allenes. Methanol additive was found to improve both the yield and enantioselectivity of the reaction. 1H NMR studies show that methanol exchanges with the pinacol ligand on the boron “ate” complex
Thesis (PhD) — Boston College, 2020
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry

35

Son, Eun-Cheol. "Exploitation of some palladium-catalyzed coupling reactions of aryltriazenes or arylsilicon compounds." 京都大学 (Kyoto University), 2006. http://hdl.handle.net/2433/144020.

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Kyoto University (京都大学)
0048
新制・課程博士
博士(工学)
甲第12334号
工博第2663号
新制||工||1376(附属図書館)
24170
UT51-2006-J326
京都大学大学院工学研究科物質エネルギー化学専攻
(主査)教授小澤文幸, 教授檜山爲次郎, 教授杉野目道紀
学位規則第4条第1項該当

36

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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37

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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38

劉曉霞 and Xiaoxia Liu. "Coordination Chemistry of 1,2-naphthoquinone-mono-oxime withruthenium, rhodium and palladium." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2000. http://hub.hku.hk/bib/B3124063X.

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39

Liu, Xiaoxia. "Coordination Chemistry of 1,2-naphthoquinone-mono-oxime with ruthenium, rhodium and palladium /." Hong Kong : University of Hong Kong, 2000. http://sunzi.lib.hku.hk/hkuto/record.jsp?B2168781X.

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40

Dostert, Karl-Heinz. "Selectivity in hydrogenation of alpha, beta-unsaturated carbonyl compounds on model palladium catalysts." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät, 2015. http://dx.doi.org/10.18452/17399.

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Die Umsetzung von alpha,beta-ungesättigten Aldehyden und Ketonen mit Wasserstoff über Pd-Modellkatalysatoren wurde anhand von Molekularstrahlmethoden, kombiniert mit Infrarot-Reflexions-Absorptions-Spektroskopie (IRAS), Quadrupol-Massenspektrometrie (QMS) und Röntgen-Nahkanten-Absorptions-Spektroskopie (NEXAFS), unter wohldefinierten Ultrahochvakuumbedingungen untersucht. Das Ziel dieser Arbeit war es, ein atomistisches Verständnis der strukturellen Faktoren zu gewinnen, die die Aktivität und Selektivität eines Pd(111)-Einkristalls und Eisenoxid-geträgerter Pd-Nanopartikel für die Hydrierung der C=C- und C=O-Bindungen bestimmen. Exemplarisch für diese Art von Kohlenwasserstoffen wurden das Aldehyd Acrolein und das Keton Isophoron gewählt. Die NEXAFS- und IRAS-Studien zeigten, dass Isophoron bei niedrigen Bedeckungen auf Pd(111) in einer flachliegenden Geometrie adsorbiert wird. Die Neigungswinkel der C=C- und C=O-Bindungen in Bezug auf die Pd(111)-Ebene nehmen mit zunehmender Oberflächenbedeckung zu. Auf reinem Pd(111) ist die Neigung der C=C-Bindung stärker ausgeprägt, was auf eine Verzerrung des konjugierten pi-Systems hindeutet. Bei Anwesenheit von Wasserstoff wird eine schwächere Bindung von Isophoron an Pd beobachtet. Die selektive partielle Hydrierung über einer Pd(111)-Oberfläche und geträgerten Pd-Nanopartikeln unterschiedlicher Größen wurde unter Verwendung von Acrolein untersucht. Molekularstrahlmethoden wurden mit IRAS- und QMS-Messungen kombiniert, um gleichzeitig die Bildung von Adsorbaten auf der Oberfläche und die der Produkte in der Gasphase verfolgen zu können. Über einem Pd(111)-Kristall wird Propenol mit nahezu 100% Selektivität durch Hydrierung der C=O-Gruppe gebildet, während über Pd-Partikeln Propanal durch selektive Hydrierung der C=C-Gruppe erzeugt wird. IRAS-Untersuchungen zeigten, dass die Propenol-Bildung eine Modifikation der Pd(111)-Oberfläche mit einer dichten Oxopropyl-Monolage voraussetzt.
The conversion of alpha,beta-unsaturated aldehydes and ketones with hydrogen over model Pd catalysts was investigated using molecular beam techniques combined with infrared reflection-absorption spectroscopy (IRAS), quadrupole mass spectrometry (QMS), and near-edge X-ray absorption fine structure (NEXAFS) studies under well-defined ultra-high vacuum conditions. The aim of this work was to gain atomistic-level understanding of structural factors governing the selectivity and activity of a Pd(111) single crystal and iron-oxide-supported Pd nanoparticles for C=C and C=O bond hydrogenation. The ketone isophorone and the aldehyde acrolein were chosen as prototypical alpha,beta-unsaturated carbonyl compounds. NEXAFS and IRAS studies showed that isophorone is adsorbed on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C=C and C=O bonds tilt with respect to the surface plane. The tilting is more pronounced for the C=C bond on pristine Pd(111), indicating a strong distortion of the conjugated pi system upon interaction with Pd. Co-adsorbed hydrogen leads to a conservation of the in-plane geometry of the conjugated pi system, pointing to a much weaker interaction of isophorone with Pd in the presence of hydrogen. The selective partial hydrogenation over a Pd(111) surface and supported Pd nanoparticles with different particle sizes was investigated using acrolein. Molecular beam techniques were combined with IRAS and QMS measurements in order to simultaneously monitor the evolution of surface species and the formation of the final gas-phase products. Over a Pd(111) single crystal, acrolein is hydrogenated at the C=O bond to form propenol with nearly 100% selectivity, while over supported Pd particles, selective conversion of the C=C bond to propanal occurs. IRAS investigations showed that a distinct modification of the Pd(111) surface with a dense overlayer of an oxopropyl species is required for propenol formation.

41

Akintomide, Temiloluwa Selby Trent Dale. "Synthesis, characterization and properties of rigid macromolecules with extended conjugation, using palladium-catalyzed, alkynylated polyhaloarenes." [Denton, Tex.] : University of North Texas, 2007. http://digital.library.unt.edu/permalink/meta-dc-5206.

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42

Tang, Hau-san. "Design and synthesis of metal phosphine complexes of palladium(II) and gold(I) with various receptor ligands for ion-controlled or photoresponsive host-guest chemistry." Click to view the E-thesis via HKUTO, 2006. http://sunzi.lib.hku.hk/hkuto/record/B37877422.

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43

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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44

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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45

Banini, Serge R. "Palladium-catalyzed syntheses of indoles, pyrroloindoles, quinolines a base-mediated formation of N-alkoxyindoles, and progress toward the first total synthesis of echinosulfone A /." Morgantown, W. Va. : [West Virginia University Libraries], 2008. https://eidr.wvu.edu/etd/documentdata.eTD?documentid=5710.

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Abstract:

Thesis (Ph. D.)--West Virginia University, 2008.
Title from document title page. Document formatted into pages; contains xv, 275 p. : ill. Includes abstract. Includes bibliographical references (p. 107-113).

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Açıkel, Müge Artok Levent. "Silica Supported N-Heterocyclic Carbenes:Active and Reusable Heterogeneous Catalysts for Mizoroki-Heck Reactions/." [s.l.]: [s.n.], 2004. http://library.iyte.edu.tr/tezler/master/kimya/T000496.pdf.

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47

Dohanosova, Jana. "Domino reactions. Asymmetric palladium(II)-catalyzed cyclizations-carbonylations in the synthesis of natural compounds." Thesis, Paris 11, 2012. http://www.theses.fr/2012PA112082/document.

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La réaction de cyclisation de type Wacker, de composés polyols et aminopolyols insaturés constitue un outil puissant et efficace pour la synthèse d’hétérocycles oxygénés ou azotés.Dans ce travail de thèse, nous proposons l’étude d’une réaction catalysée par un complexe de palladium(II) de type domino-cyclisation, mettant en jeu une réaction de couplage. Cette séquence catalytique revient à une fonctionnalisation d’un hétérocycle par une chaîne latérale, tout en créant deux centres stéréogènes en une seule étape. L’influence de la nature des réactifs mis en jeu, ainsi que des conditions expérimentales sur l’activité et la diastéréosélectivité de la réaction sont discutées. Les applications vers la synthèse de produits naturels (anisomycine) ou d’analogues (varitriol) sont présentées.La réaction d’oxycarbonylation catalysée par un complexes de palladium(II) est une transformation intéressante de polyols insaturés en lactones bicycliques, présentant un motif de type tétrahydrofurane avec une excellente stéréosélectivité-cis. Le premier exemple de réaction d’oxycarbonylation catalysée par des complexes de palladium chiraux dans les liquides ioniques est décrit. Une étude approfondie de la nature des ligands démontre que les bis(oxazolines) chirales constituent les meilleurs ligands du palladium pour la cyclisation du pent-4-ène-1,3-diol racémique 69a. Le dédoublement cinétique du composé 69a sous atmosphère de monoxyde de carbone, en présence d’un complexe chiral de palladium(II) et de p-benzoquinone employant l’acide acétique ou le liquide ionique [bmim]NTf2 comme solvant, a permis d’isoler le 2,6-dioxabicyclo-[3.3.0]octane-3-ones avec jusqu’à 57% d’excès énantiomérique pour l’énantiomèrede configuration (R,R)-70a, et jusqu’à 80% d’excès énantiomérique pour l’énantiomèrede configuration (S,S)-70a
Intramolecular Wacker-type cyclization of unsaturated polyols and aminopolyols represents a powerful method in the synthesis of oxygen- or nitrogen-containing heterocycles. The thesis offers an insight into the systematic study of domino intramolecular palladium(II)-catalyzed cyclization and coupling reaction allowing the implementation of side chains into heterocyclic skeletons along with the formation of two stereocenters in a single step. Different types of coupling partners and reaction conditions were examined, the influence of substrate substituents on diastereoselectivity is discussed. The applications in the synthesis of naturally occuring compounds or their analogs are outlined (anisomycin, varitriol). Palladium(II)-catalyzed oxycarbonylation represents an interesting transformation of unsaturated polyols into bicyclic lactones with tetrahydrofuran structural motif with excellent cis-stereoselectivity. The first example of the use of ionic liquids as reaction media in the asymmetric Pd(II)-catalyzed oxycarbonylation is described. Based on a ligand screening, the chiral bis(oxazoline)-type ligands were successfully used in the Pd(II)-promoted bicyclisationof racemic pent-4-ene-1,3-diol (±)-69a. The kinetic resolution of (±)-69a in the presenceof chiral catalyst and p-benzoquinone under carbon monoxide atmosphere using acetic acid and/or ionic liquid as solvent afforded enantioenriched 2,6-dioxabicyclo[3.3.0]octane-3-ones(R,R)-70a (57% ee) and (S,S)-70a (80% ee), respectively

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Otsuka, Shinya. "Studies on Catalytic Transformations of Organosulfur Compounds via C-S Bond Cleavage." Kyoto University, 2019. http://hdl.handle.net/2433/242625.

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49

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.

50

Daghriri, Hassan. "Studies on Tumour Active Compounds with Multiple Metal Centres." Thesis, The University of Sydney, 2003. http://hdl.handle.net/2123/595.

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Abstract:

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.

Dissertations / Theses on the topic 'Palladium compounds'

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