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Dissertations / Theses on the topic 'Paladium and Copper Complexes'

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Published: 6 September 2023

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1

Broch, Fernanda. "Síntese, cristalografia e propriedades de ligantes triazenos mono e biscatenados e derivados complexos de Cu(II), Ni(II) e Pd(II)." Universidade Federal de Santa Maria, 2013. http://repositorio.ufsm.br/handle/1/4248.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior<br>Triazenes are a class of compounds characterized by the presence of a diazoamino functional group (N=N N) showing remarkable ability to support the stereochemical requisites of a wide variety of metal transition complexes. They act as versatile ligands in coordination chemistry when deprotonated and have relevant biological and synthetic porperties. This work presents the synthesis and investigation of molecular and crystal structure of a new series of monotriazenes [3-(4-phenyldiazenyl)-1-(2-fluorophenyl)triazene (2b); 1-(2-chlorophenyl)-3-(4-phenyldiazenyl)triazeno (2c), 1-(2-bromophenyl)-3-(4-phenyldiazenyl)triazene (2d); 3-(4-phenyldiazenyl)-1-(2-iodophenyl) triazene (2e); 1,3-bis-(3-methoxy-4-methylbenzoate)triazene (2g)] and substituted 1,4-bis (phenyltriazenyl)butanes, C6H5N(H)=N-N(CH2)4-N=NN(H)C6H5, [1,4-bis(4-ethyl-benzoato triazenyl) butane (5a), 1,4-bis(2-fluorophenyltriazenyl)butane (5b), 1,4-bis(2-clorophenyltriazenyl)butane (5c), 1,4-bis(2-bromophenyltriazenyl)butane (5d), 1,4-bis(2-iodophenyltriazenyl)butane (5e), 1,4-bis(4-amidophenyltriazenyll)butane (5f)]. The insertion of groups on phenyl rings attached to the triazene chains makes the environment significantly more interesting coordination providing the supramolecular array through noncovalent intermolecular interactions and self-organizatinal units of primary molecule. The metal ions used for complexation are salts of Ni2+, Cu2+ and Pd2+ and they were chosen due to the attracting biological relevance, magnetic properties, catalytic yielding. Nine metal complexes unpublished were synthesized [trans-[PdII(C6H5NNC6H4NNNC6H4Cl)2(C5H5N)2] (3c) [(PdII (R1R2C6H3NNNC6H3R1R2)(PPh3)2Cl) DMSO] [R1 = 4-C(O)OCH3, R2 = 3-OCH3] (3g) [CuII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = C2H5C(O)O (6a), R = F (6b), R = NH2C(O) (6f)], [NiII (RC6H5NNN(CH2)4NNNC6H5R)]2 [R = F (7b) R = Cl (7c) R = Br (7d) R = NH2C(O) (7f)]. The synthesis and characterization of these compounds is justified by the exploration of the reactivity, the coordinative behavior and by the understanding of the interactions between different ligands and metal centers. The structural analysis of the synthesized compounds by X-ray diffraction on single crystal in the solid state were performed for characterization of interactions in the crystal. Thus, a thorough understanding of the relationship between the crystal structure and supramolecular organization is analyzed. Besides the structural analysis of compounds, elemental analysis CHN, infrared, nuclear magnetic resonance and ultraviolet-visible spectroscopies and mass spectrometry were also carried out for characterization. The physical chemical properties were investigated through thermogravimetric analysis and magnetic susceptibility.<br>Triazenos são importantes membros da família de compostos nitrogenados de cadeia aberta, caracterizados por conter o grupo funcional [N═N─N] e apresentam diferentes propriedades de coordenação a metais de transição. São compostos fracamente ácidos e quando desprotonados atuam como ótimos ligantes na química de coordenação apresentando grande importância sintética e biológica. Nessa tese, foi inicialmente desenvolvida a síntese de uma série inédita de compostos triazenos monocatenados [3-(4-fenildiazenil)-1-(2-fluorofenil)triazeno (2b); 1-(2-clorofenil)-3-(4-fenildiazenil)triazeno (2c); 1-(2-bromofenil)-3-(4-fenildiazenil)triazeno (2d); 3-(4-fenildiazenil)-1-(2-iodofenil)triazeno (2e); 1,3-bis(3-metoxi-4-metilbenzoato)triazeno (2g)] e de compostos triazenos biscatenados derivados do 1,4-bis(feniltriazenido)butano, C6H5N(H)N=N-(CH2)4-N=N-N(H)C6H5, [1,4-bis(etil-4-benzoatotriazenil) butano (5a); 1,4-bis(2-fluorofeniltriazenido)butano (5b); 1,4-bis(2-clorofeniltriazenido)butano (5c); 1,4-bis(2-bromofeniltriazenido)butano (5d); 1,4-bis(2-iodofeniltriazenido)butano (5e); 1,4-bis(4-amidofeniltriazenido)butano (5f)]. A inserção de grupamentos substituintes nos anéis fenila na cadeia triazenídica tornam o ambiente de coordenação significativamente mais interessante, propiciando o aumento da ocorrência de interações intermoleculares não covalentes e impondo a auto-organização de unidades moleculares primárias no estado sólido. Os metais escolhidos para complexação foram sais de Ni2+, Cu2+ e Pd2+ em virtude de atraírem atenção como objeto de estudos relacionados com medicina, propriedades magnéticas e catálise obtendo-se como resultados deste trabalho nove complexos metálicos inéditos [trans-[PdII(C6H5NNC6H4NNNC6H4Cl)2(C5H5N)2] (3c); [(PdII(R1R2C6H3NNNC6H3R1R2)(PPh3)2Cl)·DMSO] [R1 = 4-C(O)OCH3, R2 = 3-OCH3] (3g); [CuII(RC6H5NNN(CH2)4NNNC6H5R)]2 [R = C2H5C(O)O (6a); R = F (6b); R = NH2C(O) (6f)] ; [NiII(RC6H5NNN(CH2)4NNNC6H5R)]2 [R = F (7b); R = Cl (7c); R = Br (7d); R = NH2C(O) (7f)]. A síntese, e a caracterização desses novos compostos estão relacionadas à exploração da reatividade, ao comportamento coordenativo e a compreensão das interações entre os diferentes centros metálicos e os ligantes. Efetuou-se um estudo estrutural no estado sólido para a caracterização das interações presentes nas estruturas cristalinas dos compostos sintetizados e a ferramenta utilizada foi à difração de raios X em monocristal. Dessa forma aprofundou-se a compreensão da relação entre a estrutura cristalina e sua organização supramolecular. Além do método de difração de raios X de monocristal os compostos foram caracterizados por espectroscopia de infravermelho, espectroscopia de ressonância magnética nuclear, 1H e 13C, espectroscopia ultravioleta e visível, espectrometria de massas e análise elementar CHN. As propriedades físico-químicas foram investigadas através de análise termogravimétrica e susceptibilidade magnética.
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2

Dearling, Jason L. J. "Hypoxia targeting copper complexes." Thesis, University of Kent, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.297352.

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3

Lu, Qin. "Copper complexes of polyazacryptands." Thesis, Open University, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.298997.

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4

Salaudeen, Abibat Abisola. "Switchable iron and copper complexes." Thesis, University of Leeds, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.522980.

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5

Heslop, Julia M. "Copper complexes with potential radiopharmaceutical applications." Thesis, University of Oxford, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.418800.

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6

Ashfield, Laura. "Copper complexes with potential biomedical applications." Thesis, University of Oxford, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.426384.

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7

Trotter, Katherine D. "Copper complexes as putative contrast agents." Thesis, University of Strathclyde, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.538815.

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8

Taylor, Michelle K. "Copper complexes as putative imaging agents." Thesis, University of Strathclyde, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.424316.

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9

Hueting, Rebekka. "Radiolabelled copper complexes for cancer imaging." Thesis, University of Oxford, 2011. http://ora.ox.ac.uk/objects/uuid:47438968-6aa3-41f5-82b4-9121dc327b53.

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Chapter One introduces molecular irnaging and the modalities available for oncological irnaging. The radioisotopes and imaging agents for Positron Emission Tomography (PET) and Single Photon Emission Computed Tomography (SPECT) are discussed together with the bifunctional chelator approach for radio labelling of biomolecules. Finally, the chemistry and radioisotopes of copper are described, and copper bis(thiosemicarbazonato) complexes introduced in the context of PET irnaging. Chapter Two describes the synthesis and characterisation of novel carboxylate- and maleirnide- functionalised bis(thiosemicarbazonates) and their conjugation to biologically active molecules. Radiolabelling of a chelator-bombesin conjugate demonstrated site-specific labelling at room temperature and preliminary in vitro and in vivo studies confirmed its potential as an imaging agent. Bioconjugation to a model protein and subsequent radiolabelling was also investigated. Chapter Three introduces molecular irnaging of hypoxia with a focus on CuATSM. An overview of the currently accepted mechanism of hypoxia selectivity is presented. The emphasis is placed on the relationship between oxygenation status, uptake and retention which display cell- and tumour- line dependency. Chapter Four presents the synthesis of copper bis(thiosemicarbazonates), radiolabelled either at the metal (64CU) or at the ligand e8F or 123n for mechanistic studies. The physicochemical characteristics of the copper complexes were measured and the complexes evaluated for their in vitro hypoxia selectivity. Chapter Five describes in vitro and in vivo studies of the orthogonally radiolabelled complexes, inclusive of control experiments with [64Cu]CuATS~, the radiolabelled proligand and [64CU]CU2+ salts. In vitro cellular assays, as well as in vivo biodistribution studies including dynamic PET and SPECT were performed. Stability studies contrasting the in vitro and in vivo behaviour were carried out. The collective data suggest that the currently proposed redox trapping mechanism might not provide a full understanding of the factors governing biodistribution and tumour uptake. Chapter Six contains full experimental details for the work described in this thesis.
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10

Karabaeva, Kanykey E. "Photochemistry of dipyridyl-phenanthrenedioxin-copper complexes." Bowling Green State University / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1530026213399288.

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11

Pateman, Andrew Glen. "Copper catalysed aziridination reactions." Thesis, University College London (University of London), 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.314288.

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12

Dohanosova, Jana. "Réactions domino. Réactions de cyclisation-carbonylation asymétrique catalysées par complexes de paladium(II) dans la synthèse des produits naturels." Phd thesis, Université Paris Sud - Paris XI, 2012. http://tel.archives-ouvertes.fr/tel-00703209.

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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.
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13

Mao, Zhong. "Effects of copper-ligand and copper-copper interactions on excited state properties of luminescent copper (I) complexes : structural and photophysical studies /." View the Table of Contents & Abstract, 2003. http://sunzi.lib.hku.hk/hkuto/record/B26450859.

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14

Mao, Zhong, and 毛中. "Effects of copper-ligand and copper-copper interactions on excited state properties of luminescent copper (I) complexes: structural and photophysical studies." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2003. http://hub.hku.hk/bib/B45015582.

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15

Essex, Sarah Jane. "Spectral intensities in planar copper(II) complexes." Thesis, University of Cambridge, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239622.

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16

Theobald, Mark Brian Michael. "New copper-64 complexes for imaging hypoxia." Thesis, University of Oxford, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.555310.

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Chapter One gives an overview of medical imaging techniques, focusing on and comparing the nuclear imaging techniques of single photon emission computed tomography (SPECT) and positron emission tomography (PET). The applications of copper radioisotopes in nuclear medicine are presented, in particular the development of copper bis(thiosemicarbazonate) complexes for use as hypoxia imaging agents. Hypoxia and current strategies for its diagnosis are also discussed. Chapter Two describes the introduction of a new linker to bis(thiosemicarbazone) ligands along with the subsequent synthesis and characterisation of the zinc(II) and copper(II) complexes. The functionalisation with a simple amino acid as a comparison with a different linker group is discussed, along with the radiolabelling with copper-64, in vitro and in vivo uptake experiments. The synthesis and characterisation of new ligands incorporating two linker groups is described, with the in vitro hypoxia uptake investigated Chapter Three presents a series of novel asymmetric ligands replacing one thione sulphur donor in the N2S2 bis(thiosemicarbazone) donor set with alternative donors. The synthesis and properties of the zinc(II), copper(II) and nickel(II) complexes are described and compared against those of the analogous bis(thiosemicarbazonate) complexes. The radiolabelling with copper-64 of these compounds is discussed as well as in vitro and in vivo uptake experiments. Chapter Four discusses the synthesis and characterisation of new compounds with further modifications to the bis(thiosemicarbazone) core structure. New groups are introduced to one of the ligands investigated in Chapter 3 to increase its functionality and some investigations with other radiochemically relevant metals are carried out. Symmetric N4 donor ligands and their complexes are also discussed along with preliminary investigations into N-methylated thiosemicarbazone ligands. Chapter Five describes the functionalisation of bis(thiosemicarbazone) ligands with fluorophores to allow the subcellular distribution of the copper(II) complex to be explored. The use of two photon fluorescence and fluorescence lifetime imaging microscopy (FLIM) to distinguish between the bis(thiosemicarbazone) ligand and copper(II) complex in vitro is discussed. Chapter Six gives a summary of the results described in Chapters Two to Five. Chapter Seven contains full experimental details of the work presented in this thesis.
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17

Milne, Paul Edward Young. "Polynuclear copper-lanthanoid complexes of pyridone ligands." Thesis, University of Edinburgh, 1993. http://hdl.handle.net/1842/15394.

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The crystal structures of several copper and mixed copper-lanthanoid complexes are reported, using the 6-chloro and 6-methyl derivatives of 2-pyridone as a ligand. With 6-chloro-2-pyridone, a novel dimeric copper complex results, which has been structually and physically studied. This species, under certain conditions, exhibits a dissociation reaction which has been examined using U.V.-vis. and E.P.R. spectroscopy and by cyclic voltammetry. Reaction of this dimeric copper compound with methanol and ethylene glycol results in the formation of tetranuclear and polymeric copper complexes respectively, which have both been structurally characterised. The reaction of this copper dimer with various lanthanoids results in the formation of a series of mixed copper-lanthanoid species based on four structural types. Reactions in methanol dichloromethane result in three structural configurations depending on size of the lanthanoid used (with La and Ce, LnCu<SUB>3</SUB> with five ligands; with Gd, Dy and Er LnCu<SUB>3</SUB> with eight ligands and for Yb Ln<SUB>2</SUB>Cu<SUB>2</SUB> with four ligands). The reaction of lanthanum with the dimeric copper species in a variety of solvents gave a further two structures, one of which (in ethanol) has a similar structure to those observed with Gd, Dy and Er in methanol, while in acetonitrile a fourth structural type occurs, based on La<SUB>2</SUB>Cu<SUB>2</SUB> with six ligands. With the 6-methyl-2-pyridone an unusual hexanuclear 'metallocrown' results, which has been characterised structually and by proton and sodium-23 NMR. The reaction of this species with lanthanoids in methanol yields a range of closely related mixed copper-lanthanoid compounds all based on Ln<SUB>2</SUB>Cu<SUB>2</SUB> (as seen for the product of Yb with the copper dimer in methanol). The only difference between the structures is a change in the coordination number of the lanthanoid between Sm and Gd to accommodate the contraction in lanthanoid size. The mixed phase reaction of this 'metallocrown' with lanthanum nitrate yields an extremely remarkable structure based on a La<SUB>8</SUB>Cu<SUB>12</SUB> core.
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18

Coombs, Timothy David. "Copper complexes of functionalised N-donor ligands." Thesis, University of Bath, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.394172.

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19

LO, PRESTI ELIANA. "CHIRAL COPPER COMPLEXES AS TYROSINASE BIOMIMETIC SYSTEMS." Doctoral thesis, Università degli studi di Pavia, 2017. http://hdl.handle.net/11571/1203322.

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20

Woollard-Shore, John. "Towards functional models of copper metalloenzymes." Thesis, University of Essex, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.364506.

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21

Fotsing, Kamte Marcellin M. "Electrosynthesis and mechanism of copper(I) nitrile complexes." [S.l. : s.n.], 2004. http://deposit.ddb.de/cgi-bin/dokserv?idn=974106666.

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22

Claughton, Hannah J. "Towards radiopharmaceuticals based on copper bis(thiosemicarbazone) complexes." Thesis, University of Oxford, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.442381.

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23

Roach, Benjamin David. "Phenolic oxime copper complexes : a gas phase investigation." Thesis, University of Edinburgh, 2011. http://hdl.handle.net/1842/7582.

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This thesis explores the use of mass spectrometry to define the strengths, and understand solution phase speciation of phenolic oxime-based solvent extractants of the types used in the hydrometallurgical recovery of copper. Chapter 1 reviews briefly the current extraction technology for copper and focuses on hydrometallurgy and the use of phenolic oximes such as 5-nonylsalicylaldoxime. The modification of the latter to improve extraction efficiency is discussed, focussing on the introduction of X-substituents in the 3 position of the benzene ring. Modern mass spectrometry techniques are also discussed with a focus on their application to inorganic systems and their use in achieving the aims of this thesis, as defined above. The work described in chapter 2 involves the development of collision induced dissociation (CID) techniques to determine the relative gas phase stabilities of copper complex anions of the type [Cu(L)(L-H)]-, where LH is a 5-alkyl-3-X-2- hydroxybenzaldehyde oximes and X a range of substituents. The importance of interligand interactions in the outer-coordination sphere and their influence on gas phase anion stability, as defined by CID, is reported. The work described in Chapter 2 on CID is extended in chapter 3 and looks at the effect of charge, of ligand type, LH, and of the nature of the metal on the stability of ionic forms of [M(L)2] complexes, where LH is extended to include 5-alkyl-2- hydroxyphenylethanone oximes. The effects of substitution at the azomethine carbon atom and at the 3-position of the benzene ring and of variation of the nature of the metal on the ion dissociation mechanisms are shown to have a major influence on ion stability under CID conditions. In chapter 4 density functional theory calculations have been used to investigate the influences of substitution at the azomethine carbon atom and at the 3-position of the benzene ring and of variation of the nature of the metal on the gas phase structures of the neutral complexes, [M(L)2]. Gas phase deprotonation and dimerisation enthalpies of the ligands, LH, and enthalpies of formation of [M(L)2] complexes have been calculated and correlates with experimentally determined ligand extraction strength. The ligand type has been extended to include 3-X-2-hydroxybenzaldehyde hydrazones, which have previously been shown to have lower distribution coefficients for copper than the analogous 3-X-substituted oximes. The calculated gas phase formation enthalpies for [M(L)2] show a strong correlation with the strengths as extractants LH, measured as their pH0.5 values for metal uptake. Chapter 5 considers whether mass spectrometry can be used to define the solution equilibria when two different oxime-based ligands, LXH and LYH, compete for Cu(II) in a single phase solution. It has been established that shifts in the relative peak intensities of deprotonated ions derived from the Cu(II) complexes, [Cu(LX)2], [Cu(LY)2] and [Cu(LX)(LY)] reflect changes in the solution composition. The work described in chapter 6 extends the study of solution phase speciation using mass spectrometry. When the Cu(II) and proton concentrations of solutions were varied distinct changes in the resulting electrospray mass spectra were observed and the resulting species were identified using CID and high resolution mass spectrometry. A novel, [Cu3(L-H)3-μ3-O/OH]- species is determined to be a major component of solutions where Cu(II) concentrations are equal to/greater than the LH concentration. Various 3-X-2-hydroxybenzaldehyde oximes (X = CH2NR2) were synthesised. The incorporation of a protonatable arm in the 3-position enabled trinuclear complexes, [Cu3(L-H)3-μ3-OH], to be isolated and fully characterized, including two X-ray determined crystal structures.
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24

Strassl, Florian [Verfasser]. "Copper Dioxygen Complexes for Multiphase Flows / Florian Strassl." München : Verlag Dr. Hut, 2019. http://d-nb.info/1194289118/34.

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25

Quinlan, D. J. "Hydrogen bonding in N-ligated copper(II) complexes." Thesis, University of Nottingham, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262983.

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26

Sylvestre, Isabelle. "Copper complexes of new biologically relevant phenol ligands." Thesis, University of Leeds, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.410895.

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27

Baxter, Christopher W. "Synthesis and structural studies of polynuclear copper complexes." Thesis, University of Edinburgh, 2004. http://hdl.handle.net/1842/14925.

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This thesis investigates the effect of varying the ligand component in a cluster forming reaction recently developed for the synthesis of molecules with general formula, [Cu<sub>x+y</sub>(C≡CR)<sub>x</sub>(hfac)<sub>y</sub>] where hfac is 1,1,1,5,5,5-hexafluoropentanedione and C≡CR is a straight chain terminal alkynyl ligand (R = -C<sub>3</sub>H<sub>7</sub>, -C<sub>4</sub>H<sub>9</sub>, -C<sub>5</sub>H<sub>11­</sub>, - C<sub>6</sub>H<sub>13</sub>). Using the ‘bulky’ alkynyl ligands, 3,3-dimethyl-1-butyne (<sup>t</sup>BuC≡CH) and trimethylsilylacetylene (Me<sub>3</sub>SiC≡CH) has led to the successful isolation of five clusters containing ten or twelve copper atoms. These molecules are structurally related to a family with formula, [Cu<sub>4</sub>(aryl)<sub>4</sub>] and display an alkynyl bridged Cu<sub>4</sub> central core ‘capped’ by peripheral Cu-hfac chelate rings. Six additional clusters are reported that have nuclearities ranging between sixteen and twenty-six copper atoms. These were obtained by replacing hfacH with the trifluorinated 1,3-diketonyl ligands, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, (Ph-tfacH), 4,4,4-trifluoro-1-phenyl-1,3-butanedione (<sup>t</sup>Bu-tfacH) and 1,1,1-trifluoro-2,4-pentanedione (tfacH) or using 3,3-dimethyl-1-butyne (<sup>t</sup>BuC≡CH) or 3-phenyl-1-propyne (PhCH<sub>2</sub>C≡CH) in the cluster forming reaction. The new additions to the [Cu<sub>x+y</sub>(C≡CR)<sub>x</sub>(hfac)<sub>y</sub>] family of molecules are diverse in nuclearity and display interesting structural features. Using alkynyl or 1,3-diketone ligands with bulky substituents affects the ability of the clusters to adopt a ‘conventional’ structure and as a result interesting structural variations are observed. Using ligands with substituents that are able to form weak but significant π-stacking type intramolecular interactions also causes a distortion from a ‘conventional’ structure. There is an interesting common structural motif that appears throughout the [Cu<sub>x+y</sub>(C≡CR)<sub>x</sub>(hfac)<sub>y­</sub>] family. This motif has the formula, [Cu<sub>4</sub>(C≡CR)<sub>4</sub>(Cu-hfac)<sub>x</sub>] and all the clusters in the series are found to contain one, two or three such fragments.
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28

Voyé, Alexander. "Diamino diamide copper complexes as anti-arthritic agents." Doctoral thesis, University of Cape Town, 1993. http://hdl.handle.net/11427/17515.

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Includes bibliographical references.<br>This thesis describes the investigation of a series of diamino diamide copper(II) complexes with respect to their potential as anti-inflammatory agents in the treatment of rheumatoid arthritis. Several physico-chemical techniques were employed in the investigation including glass electrode potentiometry, UV/VIS spectroscopy, molecular mechanics calculations, speciation modelling as well as X-ray crystallography. Animal experiments were also carried out.
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29

Wang, Jun. "Silica Supported Copper Complexes and their Biomimetic Activities." W&M ScholarWorks, 2003. https://scholarworks.wm.edu/etd/1539626826.

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30

Bahgat, Sofi-Rosamelia. "Beta-diketiminato copper complexes in C-H bond amination." Connect to Electronic Thesis (CONTENTdm), 2010. http://worldcat.org/oclc/646165084/viewonline.

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31

Bell, Zoe Rachel. "Lanthanide and copper complexes of new multidentate encapsulating ligands." Thesis, University of Bristol, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324327.

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32

Mickenberg, Seth F. (Seth Fox). "Tuning the photophysical properties of amidophosphine complexes of copper." Thesis, Massachusetts Institute of Technology, 2009. http://hdl.handle.net/1721.1/49753.

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Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2009.<br>Vita.<br>Includes bibliographical references (leaves 23-24).<br>A series of monomeric copper complexes that allow for the tuning of the emission properties is reported. Luminescence lifetimes up to 150 [mu]s are observed in benzene solution at ambient temperature, which are comparable to the lifetimes of the longest-lived previously reported copper luminophores. These complexes also exhibit quantum yields up to 0 = 0.70 at 298 K. The results of time-dependent density functional theory (TDDFT) calculations indicate emission from a triplet state in all cases. The calculations also successfully correlate the energy of the transition from this triplet state to the energy of the observed emission. Such luminescence from a first-row metal is highly unusual, especially when considering the phosphine-based ligand framework used.<br>by Seth F. Mickenberg.<br>S.M.
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33

Dunbar, Lynsey. "The development of copper complexes as medical imaging agents." Thesis, University of Strathclyde, 2015. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=24947.

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Studies building on existing research into the development of in vivo oxidant sensors which could be used as magnetic resonance (MR) imaging agents for the early detection of oxidative stress have been carried out. A series of N₂S₂ copper macrocyclic systems have been synthesised building on previous studies. The compounds have been modified at various positions to further enhance the suitability of these species as magnetic resonance imaging agents. The modifications include the introduction of oxo and sulfur based pendant arms at the nitrogen donor atoms, the introduction electron withdrawing and electron donating groups at various positions on the ring and the use of softer donor atoms to produce an S₄ and S₃N system. The stability and suitability of the complexes were challenged using a number of techniques including spectrophotometric titrations, cyclic voltammetry and T₁ relation NMR. The stability of the copper centre of the macrocycles was challenged with a biologically relevant sequestration agent (bovine serum albumin). It was found that 5 coordinate copper macrocycles are the most stable. The electrochemical reversibility of the complexes was tested using cyclic voltammetry to identify which compounds were capable of redox reversibility. A sulfur based pendant arm complex (compound 52) showed promise. Studies using ascorbate and hypochlorite demonstrate that this compound will survive chemical reduction and re-oxidation returning an acceptable percentage reversibility. To assess the potential of all of the complexes for use as imaging agents, the effect of the complexes on the T₁ relaxation time was tested over a range of concentrations. This was compared with a Gd-DTPA control and original parent complex (compound 2). The modifications made very little difference to the T₁ relaxation times. Although the relaxivity is low the studies indicates that the modified complexes may have some viability for use and warrant further investigation.
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Hammouda, Ahmed N. H. "Development of copper peptide complexes as anti-Inflammatory drugs." Doctoral thesis, University of Cape Town, 2015. http://hdl.handle.net/11427/15744.

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Copper complexes have been reported to have anti-inflammatory activities for the alleviation of inflammation associated with rheumatoid arthritis (RA). The present study focuses on the design of new drugs that could be used to change the bioavailability of copper and hence alleviate inflammation. The ligands chosen were sarcosyl-L-histidyl-L-lysine, sarcosyl-Llysyl- L-histidine, sarcosyl-L-histidyl-L-histidine, sarcosyl-L-lysyl-L-lysine and sarcosyl-Lglycyl- L-histidine. Equilibrium constants of H+, Cu(II), Ni(II) and Zn(II) with the peptides were measured in aqueous solution at 25±0.01oC and an ionic strength of 0.15M (NaCl) using glass electrode potentiometry. The tripeptides species showed significantly different coordination behaviour. The results that Cu(II) coordinates to one amino group, two deprotonated peptides and one imidazole nitrogen atoms to give a neutral complex. The structures of the complex species were investigated using ultraviolet-visible (Uv-Vis), nuclear magnetic resonance (NMR), electrospray ionisation mass spectrometry (ESI-MS) spectroscopy as well as molecular mechanics (MM) calculations. The visible spectra obtained for the different species in solution were typical of Cu(II) and Ni(II) complexes. 1H NMR identified the active binding sites to be the imidazole nitrogen, the amide nitrogen and the terminal amino group. The imidazole nitrogen was involved in coordination first, followed by the amide and then the terminal amine groups. The ԑ-amino group of lysine did not coordinate to the Cu(II). Molecular mechanics was used to support the Cu(II) structures postulated from potentiometric and spectroscopic data. The prefered method of increasing the available pool of low molecular weight Cu(II) species in vivo is via dermal absorption. For this reason the drugs were designed so that they could be administered dermally and be selective for Cu(II) so that they do not affect the speciation of other metal ions in blood plasma. Speciation calculations of Cu(II) using a computer model of blood plasma indicated that Sar-Lys-His was the best at mobilising copper in vivo. This study also considered percutaneous skin absorption. Octanol/water partition coefficients and Franz cell permeation studies showed that the Cu(II) complexes are hydrophilic but that Sar-Gly-His caused a 2 fold increase in membrane permeability of Cu(II).
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Ireland, David Rey. "Copper(II) and Ruthenium(II) Complexes from Polydentate Ligands." University of Dayton / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1523008522727672.

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36

Vance, Michael Alan. "Spectroscopic studies of structural and functional binuclear copper model complexes of coupled binuclear copper proteins /." May be available electronically:, 2007. http://proquest.umi.com/login?COPT=REJTPTU1MTUmSU5UPTAmVkVSPTI=&clientId=12498.

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37

Ellul, Charles. "Trimetallic N-heterocyclic carbene complexes." Thesis, University of Bath, 2011. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.538279.

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38

Garrido, Barros Pablo. "Molecular Water Oxidation Catalysts Based on Copper and Nickel Complexes." Doctoral thesis, Universitat Rovira i Virgili, 2018. http://hdl.handle.net/10803/665124.

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Aquesta Tesi Doctoral es centra en l’estudi de catalitzadors moleculars per a l’oxidació d’aigua basats en coure i níquel, ja que la seva gran abundància i baix cost els fa potencials candidats pel seu ús en sistemes catalítics. Tot i així, avui en dia hi ha una important mancança d’informació respecte als seus mecanismes de reacció i els factors que influeixen la seva activitat. Per això, en primer lloc, es desenvolupen nous catalitzadors moleculars basats en el coure com a centre metàl·lic. L’estudi mecanístic d’aquests catalitzadors revela l’important rol que té l’oxidació del lligand en el cicle catalític a l’hora de controlar el sobre-potencial de la reacció. Al mateix temps, en col·laboració amb el grup del Professor Maseras (ICIQ) es descobreix un nou mecanisme per a la formació de l’enllaç oxigen-oxigen que opera en diferents tipus catalitzadors de coure. Aquest nou mecanisme sense precedents permet redefinir l’escenari mecanístic per a l’oxidació d’aigua. Posteriorment, es realitza el disseny de nous lligands amb diferents propietats redox que permeten estudiar factors que influeixen en l’activitat i el mecanisme de reacció. Això proporciona informació rellevant per al disseny de nous catalitzadors més actius, estables i eficients. També s’aborda la immobilització dels catalitzadors desenvolupats sobre els elèctrodes basats en grafè. D’aquesta manera es descobreix el paper essencial que té la deslocalització d’electrons en els orbitals π, que permet incrementar la cinètica de la reacció per més de dues ordres de magnitud. Finalment, el coneixement generat en coure s’intenta expandir per a la seva aplicació en els catalitzadors de níquel. Això permet estudiar el caràcter làbil dels complexos de níquel en medis bàsics, que determina la presència de dos mecanismes d’operació basats en espècies moleculars i òxids de níquel respectivament.<br>Esta Tesis Doctoral se centra en el estudio de catalizadores moleculares para la oxidación de agua basados en cobre y níquel, ya que su gran abundancia y su bajo coste los hace potenciales candidatos para su uso en sistemas catalíticos. A pesar de esto, hoy en día hay una importante carencia de información con respecto a sus mecanismos de reacción y los factores que determinan su actividad. Por ello, en primer lugar, se desarrollan nuevos catalizadores moleculares basados en cobre como centro metálico. El estudio mecanístico de dichos catalizadores revela el importante rol que tiene la oxidación del ligando en el ciclo catalítico a la hora de controlar el sobre-potencial de la reacción. Al mismo tiempo, en colaboración con el grupo del Profesor Maseras (ICIQ) se descubre un nuevo mecanismo para la formación del enlace oxígeno-oxígeno que opera en diferentes tipos de catalizadores de cobre. Este nuevo mecanismo sin precedentes permite redefinir el escenario mecanístico para la oxidación de agua. Posteriormente, se realiza el diseño de nuevos ligandos con diferentes propiedades redox que permiten estudiar los factores que influyen en la actividad y el mecanismo de reacción. Esto proporciona información relevante para el diseño de nuevos catalizadores más activos, estables y eficientes. También se aborda la inmovilización de los catalizadores desarrollados sobre electrodos basados en grafeno. De esta forma se descubre el papel esencial que tiene la deslocalización de electrones en orbitales π, que permite incrementar la cinética de reacción por más de dos órdenes de magnitud. Finalmente, el conocimiento generado en cobre se intenta expandir para su aplicación en catalizadores de níquel. Esto permite estudiar el carácter lábil de los complejos de níquel en medios básicos, que determina la presencia de dos mecanismos de operación basados en especies moleculares y óxidos de níquel respectivamente.<br>This Doctoral Thesis focuses on the study of molecular catalysts for water oxidation based on copper and nickel since their high abundance and inexpensive character make them potential candidates for their use in catalytic systems. Despite that, there is a current lack of information regarding their reaction mechanism and the factors that determine their activity. Therefore, we first develop new molecular catalysts based on copper as metal center. Their mechanistic study reveals the essential role that the ligand oxidation has in the catalytic cycle as tool to control the reaction overpotential. In collaboration with Prof. Maseras group (ICIQ) a new mechanism for the oxygen-oxygen bond formation is found to operate in different copper catalysts. This unprecedented mechanism allows us to redefine the mechanistic scenario in water oxidation. Later on, the design of new ligands with different redox properties is addressed. That allows to study the factors that have influence on the activity and reaction mechanism and provide valuable information for the design of more active, stable and efficient new catalysts. Moreover, the immobilization of the molecular catalyst on the surface of graphene-based electrodes is also studied. We discover the essential role of the π-delocalization in increasing the reaction kinetic by more than two orders of magnitude. Finally, the knowledge developed with copper complexes is applied in nickel catalysis. This allows to study the labile character of nickel complexes in basic media that determine the presence of two different operating mechanism based on molecular species and nickel oxides respectively.
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39

Fung, Chi-ming Kelvin. "Synthesis and applications of copper hydride complexes in reductive reactions." Click to view the E-thesis via HKUTO, 2005. http://sunzi.lib.hku.hk/hkuto/record/B36388208.

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40

Löw, Sabine [Verfasser]. "Synthesis, characterization and reactivity of Copper Cluster Complexes / Sabine Löw." Gießen : Universitätsbibliothek, 2014. http://d-nb.info/1068590750/34.

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41

Lankes, Christian [Verfasser], and Oliver [Akademischer Betreuer] Reiser. "Photoredox Catalysis Using Copper Complexes / Christian Lankes ; Betreuer: Oliver Reiser." Regensburg : Universitätsbibliothek Regensburg, 2018. http://d-nb.info/1178115178/34.

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42

Bonnitcha, Paul D. "Synthesis and evaluation of novel copper complexes to target hypoxia." Thesis, University of Oxford, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.509896.

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43

Fung, Chi-ming Kelvin, and 馮志明. "Synthesis and applications of copper hydride complexes in reductive reactions." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2005. http://hub.hku.hk/bib/B36388208.

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44

Stroud, Joanne. "Dinuclear copper complexes with planar, neutral, N-donor, bridging ligands." Thesis, University of Nottingham, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.282624.

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45

Madzivire, Cecilia Rutendo. "Ruthenium and copper complexes for anti-cancer and catalytic applications." Thesis, University of Leeds, 2018. http://etheses.whiterose.ac.uk/21035/.

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This thesis details the synthesis, characterisation and evaluation of novel β-bis-ketoiminate ruthenium(II) and β-bis-ketoiminate copper(II) complexes for their biological and chemical applications. The anti-cancer, anti-bacterial and anti-fungal and catalytic activity of these complexes was investigated, with lead complexes undergoing further mechanistic investigations. Chapter 1 contains the background introduction to the project, through literature research of similar work as well as the aims of this project. Chapter 2 presents the synthesis and characterisation of novel β-bis-ketoiminate ruthenium(II) dicarbonyl complexes. 1H NMR, 13C {1H} NMR and detailed X-ray crystallographic data are given for this series of complexes. Chapter 3 introduces novel β-bis-ketoiminate copper(II) complexes, their synthesis and characterisation, with X-ray crystallographic data discussed. Chapter 4 introduces the MTT technique for assessing cytotoxicity, and discusses the anti-cancer activities of the series of complexes synthesised in Chapters 2 and 3. In addition, the chapter gives a brief literature review to anti-bacterial and anti-microbial studies, and the results of anti-bacterial and anti-fungal investigations on the β-bis-ketoiminate ruthenium(II) and copper(II) complexes. Chapter 5 presents the results of chemical investigations, hydrolysis and biomembrane, conducted on the two libraries of complexes. Chapter 6 contains a brief literature review on catalysis, and the results for transfer hydrogenation and Ullmann catalytic reactions on β-bis-ketoiminate ruthenium(II) complexes and β-bis-ketoiminate copper(II) complexes respectively. Chapter 7 contains experimental details and characterisation data for all the complexes synthesised within this thesis, and protocols for all the biological and chemical studies. Appendix presents a summary of X-ray crystallographic structure analysis for all the crystal structures reported within this thesis.
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Betts, Helen May. "Novel copper-64 complexes for applications in positron emission tomography." Thesis, University of Oxford, 2009. http://ora.ox.ac.uk/objects/uuid:8e10fd02-8f20-43d6-8b32-d99e897257cc.

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47

Dalle, Kristian Erwin. "Bioinspired Activation of Oxygen with Pyrazole-Supported Dinuclear Copper Complexes." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2014. http://hdl.handle.net/11858/00-1735-0000-002B-7C1A-B.

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48

Betancourt, Daniel. "Copper bis(phenanthroline) complexes as simple models for molecular transducers." Tallahassee, Fla. : Florida State University, 2008. http://purl.fcla.edu/fsu/lib/digcoll/undergraduate/honors-theses/368250.

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Thesis (Honors paper)--Florida State University, 2008.<br>Advisor: Dr. Kenneth Goldsby, Florida State University, College of Arts and Sciences, Dept. of Chemistry and Biochemistry. Includes bibliographical references.
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49

Seeba, Marten. "Bioinspired dinuclear copper complexes for catalytic oxidation of phenolic substrates." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2017. http://hdl.handle.net/11858/00-1735-0000-002E-E4DC-8.

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50

Magni, M. "COPPER AND RUTHENIUM COMPLEXES IN SENSITIZED SOLAR CELLS AND OPTOELECTRONICS." Doctoral thesis, Università degli Studi di Milano, 2015. http://hdl.handle.net/2434/333099.

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In perfect harmony with the "Year of Light (IYL 2015)", the thesis has been entirely centered on the concept of Light involving the development of transition metal complexes for both the conversion of light into electric energy through dye-sensitized solar cells and, conversely, the production of light starting from electricity by fabrication of electroluminescent devices. The main part of the thesis has been devoted to the sunlight-to-electricity conversion, a target that is well contextualized within the global commitment for the progressive increase of the percentage of electric energy produced by renewable resources. In this context dye-sensitized solar cells, DSSCs, are promising devices alternative to the well established technology of silicon photovoltaics for energy production from the abundant solar light. DSSCs are devices able to harvest solar light and convert it into electricity employing a sensitizer (adsorbed on a semiconductor) and a redox couple properly chosen and combined. The project have concerned the design, synthesis and characterization of both sensitizers and redox mediators constituted by ruthenium and copper-based complexes respectively, together with their final assembly into laboratory-type DSSCs to evaluate their performance. In this way an all-round study has been carried out, from molecules on paper to test benches, passing through laboratory counters. The second, minor part, of the thesis has been focused on the diametrically opposed task, the generation of light. In this context some luminescent heteroleptic complexes based on the cheap and quite abundant copper element have been proposed. The final aim has been the synthesis of efficient luminophores for fabrication of devices able to generate light applying an electric potential across two electrodes such as in organic light-emitting diodes, OLEDs, or in analogue light-emitting electrochemical cells, LECs. The light production in LED-type devices is very efficient especially compared with other traditional artificial light sources like incandescent or fluorescent lamps, and so in line with the international policy of reducing energy consumption. In conclusion the thesis project can be schematically depicted as a circular pathway that joints together two opposite but strictly interconnected concepts (i.e. light and electricity) mutually corresponding to the task and the mean, the start and the end.
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