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1
Hussein, Hiba. "Synthèses de nouveaux ligands carbènes à structures N-hétérocycliques et macro-N-Bis-hétérocycliques symétriques et dissymétriques. Études de leurs propriétés photophysiques, biologiques et de coordination". Electronic Thesis or Diss., Université de Lorraine, 2022. http://www.theses.fr/2022LORR0014.
Abstract (sommario):
L'objectif de ce travail de thèse consiste à préparer de nouvelles molécules photosensibles de type carbènes N-hétérocycliques, ligands ou complexes, dessinées pour répondre aux critères des photosensibilisateurs (PS) (molécules pures, hydrosolubles, biocompatibles, non toxiques, d'efficacité d'absorbance maximale, possédant de bonnes propriétés photophysiques) applicables dans le domaine des matériaux ou/et dans le domaine biomédical tel qu'en photothérapie. L'ambition étant d'optimiser les propriétés spectroscopiques des photosensibilisateurs et d'obtenir une bonne photoactivité. Ce travail de thèse décrit dans un premier chapitre un état de l'art non exhaustif concernant les macrocycles hétérocycliques, les carbènes N-hétérocycliques (NHC) et les macrocycles de type NHC ainsi qu'un rappel des propriétés attendues des molécules photosensibles. Dans un deuxième chapitre, il détaille les synthèses de ligands originaux N-hétérocycliques et N-bis-hétérocycliques bis-imidazolium de structures ouvertes ou macrocycliques fermées ainsi que leurs caractérisations physico-chimiques (infrarouge, RMN, spectroscopie de masse). Des structures cristallographiques de certains de ces macrocycles ont été obtenues par diffraction des rayons X. Dans un troisième et dernier chapitre, sont détaillés les différents essais de formation des carbènes et l'étude de leurs propriétés de complexation vis-à-vis des métaux de transition. Des calculs théoriques Gaussian viennent en appui de celle-ci. Une étude par fluorescence et par production d'oxygène singulet ainsi qu'une évaluation des propriétés biologiques des macrocycles et ligands flexibles présentés précédemment, montrent des propriétés photophysiques et biologiques prometteuses. De plus, une étude préliminaire intéressante de l'échange proton/deutérium des protons carbèniques des macrocycles bis-imidazolium est décriteThe objective of this thesis is to prepare new photosensitive molecules of N-heterocyclic carbenes, ligands or complexes, designed to meet the criteria of photosensitizers (PS) (pure, water-soluble, biocompatible, non-toxic molecules, with maximum absorbance efficiency, possessing good photophysical properties) applicable in the field of materials and/or in the biomedical field such as phototherapy. The ambition is to optimise the spectroscopic properties of the photosensitisers and to obtain a good photoactivity. This thesis describes in a first chapter a non-exhaustive state of the art concerning heterocyclic macrocycles, N-heterocyclic carbenes (NHC) and NHC macrocycles as well as a reminder of the expected properties of photosensitive molecules. In a second chapter, it details the syntheses of original N-heterocyclic and N-bis-heterocyclic bis-imidazolium ligands of open or closed macrocyclic structures as well as their physicochemical characterizations (infrared, NMR, mass spectroscopy). Crystallographic structures of some of these macrocycles were obtained by X-ray diffraction. In a third and final chapter, the various tests for the formation of carbenes and the study of their complexation properties towards transition metals are detailed. Theoretical Gaussian calculations are used to support this study. A fluorescence and singlet oxygen production study as well as an evaluation of the biological properties of the previously presented flexible macrocycles and ligands show promising photophysical and biological properties. In addition, an interesting preliminary study of the proton/deuterium exchange of carbon protons of bis-imidazolium macrocycles is described.Keywords: NHC, macrocyclic ligands, bipyridine, bithiazole, imidazolium, photosensitiser, photoactivity, anti-bacterial properties
2
Weis, Philippe [Verfasser], e Ingo [Akademischer Betreuer] Krossing. "Exploring the chemistry of group 15/16 cages with weakly coordinating aluminates – synthesis and coordination chemistry of inorganic cages". Freiburg : Universität, 2019. http://d-nb.info/119056100X/34.
3
Noack, Cassandra, e n/a. "Studies in Coordination Chemistry". Griffith University. School of Science, 2003. http://www4.gu.edu.au:8080/adt-root/public/adt-QGU20031030.145610.
Abstract (sommario):
The research reported in this thesis was carried out in Brisbane, Australia and Calgary, Canada. The aim of the research conducted in Brisbane was to prepare a series of copper(I) and ruthenium(II) based complexes incorporating a hemilabile phosphine ligand and to determine whether or not these compounds possessed catalytic activity. The history, uses, properties and recent work incorporating hemilabile phosphine ligands is discussed in detail as well as the application of hemilabile ligands to atom transfer radical polymerization (ATRP) and the usefulness of the 'windscreen wiper' action of these ligands in polymerization. The literature synthesis and characterization of four hemilabile phosphine ligands is reported with modifications. The (2-chlorophenyl)diphenylphosphine ligand was prepared via a Grignard reaction giving a 11% yield. The (2-bromophenyl) diphenylphosphine ligand was prepared by reaction of 2-bromoiodobenzene with Ph2PSiMe3 in the presence of a palladium catalyst (MeCN)2PdCl2 which yielded 50% product. The 1-chloro-2-diphenylphosphinoethane ligand was prepared following the generation of a lithium diphenylphosphide which was added to 1,2-dichloroethane to give a 43% yield of product. The (2-benzoic-acid)diphenylphosphine ligand was prepared by hydrolysis of (2-methyl-ester-phenyl)diphenylphosphine. Following acidification of the methyl ester phosphine with HCl, the desired product was isolated in 88% yield. The synthesis and characterization of a series of copper(I) based complexes incorporating the prepared phosphine ligands involved reaction in CH3CN of the appropriate ligand with copper halides as starting material. Solution state 31P NMR and mass spectrometry were used to study many of these complexes in the solution state, whilst microanalysis, 31P CP MAS NMR and single crystal X-ray diffraction studies were used to study their solid state properties. The complexes of the type bis(2-halophenyl)diphenylphosphine copper halide were found to be three coordinate with non-chelating ligands and to be isostructural with the previously studied bis(2-methylphenyl)diphenylphosphine copper halide complexes. The synthesis and characterization of ruthenium(II) based complexes incorporating hemilabile phosphine ligands involved reaction of the appropriate ligands in MeOH with RuCl3.3H2O or RuCl2(DMSO)4 as the ruthenium source. Modes of characterization included solution state 31P NMR, mass spectrometry, microanalysis and single crystal X-ray diffraction studies. All ruthenium(II) based complexes were found to incorporate the hemilabile ligands in a chelating mode resulting in 6 coordinate structures. The preliminary polymerization testing of MMA in the presence of the copper(I) and ruthenium(II) based complexes has been reported. All complexes successfully polymerized the monomer and the resulting polyMMA showed polydispersity values ranging from moderate (3.1) to very high (6.7). Chapter 7 discusses research conducted over a 6 month period at the University of Calgary, Canada under an International Resident Fellowship award. This work involved the synthesis and characterization of scandium(III) and yttrium(III) based complexes incorporating a chelating amido-imine ligand, as potential olefin polymerization catalysts.
4
Noack, Cassandra. "Studies in Coordination Chemistry". Thesis, Griffith University, 2003. http://hdl.handle.net/10072/366798.
Abstract (sommario):
The research reported in this thesis was carried out in Brisbane, Australia and Calgary, Canada. The aim of the research conducted in Brisbane was to prepare a series of copper(I) and ruthenium(II) based complexes incorporating a hemilabile phosphine ligand and to determine whether or not these compounds possessed catalytic activity. The history, uses, properties and recent work incorporating hemilabile phosphine ligands is discussed in detail as well as the application of hemilabile ligands to atom transfer radical polymerization (ATRP) and the usefulness of the 'windscreen wiper' action of these ligands in polymerization. The literature synthesis and characterization of four hemilabile phosphine ligands is reported with modifications. The (2-chlorophenyl)diphenylphosphine ligand was prepared via a Grignard reaction giving a 11% yield. The (2-bromophenyl) diphenylphosphine ligand was prepared by reaction of 2-bromoiodobenzene with Ph2PSiMe3 in the presence of a palladium catalyst (MeCN)2PdCl2 which yielded 50% product. The 1-chloro-2-diphenylphosphinoethane ligand was prepared following the generation of a lithium diphenylphosphide which was added to 1,2-dichloroethane to give a 43% yield of product. The (2-benzoic-acid)diphenylphosphine ligand was prepared by hydrolysis of (2-methyl-ester-phenyl)diphenylphosphine. Following acidification of the methyl ester phosphine with HCl, the desired product was isolated in 88% yield. The synthesis and characterization of a series of copper(I) based complexes incorporating the prepared phosphine ligands involved reaction in CH3CN of the appropriate ligand with copper halides as starting material. Solution state 31P NMR and mass spectrometry were used to study many of these complexes in the solution state, whilst microanalysis, 31P CP MAS NMR and single crystal X-ray diffraction studies were used to study their solid state properties. The complexes of the type bis(2-halophenyl)diphenylphosphine copper halide were found to be three coordinate with non-chelating ligands and to be isostructural with the previously studied bis(2-methylphenyl)diphenylphosphine copper halide complexes. The synthesis and characterization of ruthenium(II) based complexes incorporating hemilabile phosphine ligands involved reaction of the appropriate ligands in MeOH with RuCl3.3H2O or RuCl2(DMSO)4 as the ruthenium source. Modes of characterization included solution state 31P NMR, mass spectrometry, microanalysis and single crystal X-ray diffraction studies. All ruthenium(II) based complexes were found to incorporate the hemilabile ligands in a chelating mode resulting in 6 coordinate structures. The preliminary polymerization testing of MMA in the presence of the copper(I) and ruthenium(II) based complexes has been reported. All complexes successfully polymerized the monomer and the resulting polyMMA showed polydispersity values ranging from moderate (3.1) to very high (6.7). Chapter 7 discusses research conducted over a 6 month period at the University of Calgary, Canada under an International Resident Fellowship award. This work involved the synthesis and characterization of scandium(III) and yttrium(III) based complexes incorporating a chelating amido-imine ligand, as potential olefin polymerization catalysts.Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Science
Faculty of Science
Full Text
5
Keene, Frank Richard. "Aspects of coordination chemistry /". Title page, contents and abstract only, 1998. http://web4.library.adelaide.edu.au/theses/09SD/09sdk26.pdf.
6
Higginson, Joshua J. "Synthesis and coordination chemistry of ditopic ligands capable of coordinating metal ions and interacting with anions". Thesis, University of Huddersfield, 2015. http://eprints.hud.ac.uk/id/eprint/26444/.
Abstract (sommario):
The aim of this research was to synthesise a series of novel organic multidentate ligands which contain N-donor domains for the coordination of metal ions and amide or amine hydrogen atoms which are capable of interaction with anions. It was envisaged that incorporation of these two binding units would produce a system where the metal ions would control the ability of the ligand to interact with anions or vice versa. Ligand 1 contains a tetradentate N-donor domain formed by a central bipyridine, two thaizole units and two amide units attached in the 4,4’-position of the bipyridine unit. Reaction of this with divalent metal ions results in a mono-nuclear complex where the metal is bound by the N-donor atoms and the amides interact with a variety of anions. Reaction with monovalent metal ions results in the formation of a dinuclear double helicate with the metal again coordinated by the N-donor domains and the anions interacting with the amide hydrogen atoms. This results in a polymeric assembly in the solid state. Ligand 2 contains an identical tetradentate domain comprised of the same N-donor units; however the single amides in the 4,4’-position have been removed and a diamide attached in the 3,3’-position of the bipyridine unit. Reaction of [L2 with divalent cations results in a similar mono-nuclear species. The metal centre is coordinated by the N-donor atoms and one of the acetyl units from two adjoining ligands with the counter ions undergoing interactions with the diamide hydrogen atoms. Coordination of the same ligand with a monovalent cation resulted in a di-nuclear double helicate, each metal centre is fulfilled by the N-donor atoms of the ligand strand and the hydrogen atoms of the diamide units interact with anions. This too results in a polymeric assembly in the solid state. Ligands 3 and 4 contain the iso-structural tetradentate N-donor domain seen in [L1] and [L2] but their functionality in the 3,3’-position differ. Ligand 3 contains a urea group while ligand 4 has a single amide group attatched to an indole unit. Coordination of [L3] and a divalent metal ion results in the formation of a mono-nuclear species with the metal ion bound by the central bipyridine and the N-donor of two thaizole units. Furthermore each of the urea groups in the 3,3’-position undergo favourable interactions with the perchlorate counter ions. A solid state structure of Ligand 4 was only successful with a monovalent cation resulting in the formation of a dinuclear double stranded species. Each metal centre exhibits a distorted trigonal planar geometry through coordination with a pyridine and thiazole ring of one strand and a single thiazole ring of another. The indole and amide of each ligand strand undergo two sets of interactions; anion interactions through the amide and indole hydrogen atoms as well as complementary intermolecular interactions between the indole N···H units of one ligand and the carbonyl C···O units of another complex. Both [L3] and [L4] exhibit long range order through favourable anion-NH interactions however [L4] also displays complimentary indole/acetyl interactions to develop a larger aggregate species. In all these cases the resultant complex is independent upon which anion is used. However, this is not the case with ligand 5. Reaction of [L5] with Cu(BF4)2 or Cu(ClO4)2 gave a dinuclear double helicate with a cleft within the helicate assembly in which an anion is bound. However, reaction of this with half an equivalent of either sulphate (SO4 2-) or dihydrogen phosphate (H2PO4 -) results in the formation of a different dinuclear double helicate whereby the cleft is occupied by either a dihydrogen phosphate or sulphate anion which bridges the metal centres. Further addition of sulphate results in no change of the ESI-MS indicating the dinuclear double helicate persist however addition of one equivalent of di-hydrogen phosphate leads to the formation of a pentanuclear circular helicate. Each metal centre is coordinated by the pyridine and thiazole units of two different ligand strands and a single Cu···O interaction from one of the dihydrogen phosphates. The inclusion of three dihydrogen phosphates into the centre of the assembly as well as a series of phosphate-ligand and phosphate-phosphate interactions leads to the dimerization of the structure with another set of phosphates from a second assembly. Further reaction of this dinuclear species with one equivalent of (Bu4N)NO3 resulted in the formation of a hexanuclear circular meso-helicate (or mesocate). In this structure each Ndonor domain of a thiazole and pyridine ring coordinate two different Cu2+ metal centres. Each metal centre exhibits a distorted octahedral arrangement with two ligand strands completing 4 of its 6 coordination sites, the remaining sites are occupied by two O-donors of a nitrate anion. In addition an amine of each ligand strand points into the centre of the complex creating a cavity capable of hosting two nitrate anions. Ligand 6 is made up of the same bis-bidentate donors as ligand 5 with the addition of a nitrogen atom into the central phenyl spacer. On reaction of [L6] with a divalent metal ion (e.g. Cu(II)) a simple mono-nuclear structure is observed. Although a mono-nuclear assembly is expected, it is interesting that even a simple change in the ligand strand can have a dramatic affect on the self-assembly process. When a central 1,3-phenylene spacer is employed (i.e. [L5]) a dinuclear double helicate is formed, however, when a 1,3-pyridine unit is contained within the ligand strand (i.e. [L6]) a simple mono-nuclear species is produced.
7
Wu, Haiying. "Coordination chemistry of tetraneopentoxyphthalocyaninatocobalt(II)". Thesis, University of British Columbia, 1991. http://hdl.handle.net/2429/29822.
Abstract (sommario):
The thesis work reports developments in the coordination chemistry of tetra-neopentoxyphthalocyaninatocobalt(II) (CoTNPc) complexes. The preparation, characterization,
and ligand binding measurements in solution of seven new compounds are described in this thesis. Some additional complexes are studied in situ.
Measurement of the equilibrium constants by UV-visible spectroscopy for the 1:1 binding reactions of the axial ligands (L = imidazole, N-methylimidazole, pyridine, 4-picoline, 4-tert-butylpyridine, piperidine, tetrahydrofuran) to CoTNPc in toluene solution allow for an estimation of the enthalpies for the binding of the N-donor ligands (7 - 12 kcal/mol) and the O-donor ligand (~ 4 kcal/mol). The order of equilibrium constants for ligand binding at room temperature is found to be: N-MeIm > pip > 4-[formula omitted]Bupy > Im > py > THF. Seven five-coordinate CoTNPc species have been isolated (L = N-MeIm, py, 4-pic, 4-[formula omitted]Bupy, pip, THF, DMSO) and characterized by elemental analyses, and UV-visible, MS (FAB), and NMR spectroscopy.
The magnetic moment of CoTNPc in the solid state is found to be 2.23 ± 0.10 B.M. at ambient temperature, while the magnetic moment is 2.47 ± 0.10 B.M. in toluene solution. The magnetic moment of the five-coordinate species (py)CoTNPc is 2.61 ± 0.10 B.M. in toluene solution. It is concluded that CoTNPc and the five-coordinate complex (py)CoTNPc at room temperature are low spin with one unpaired electron.
The ¹H NMR spectra of the paramagnetic species (CoTNPc, LCoTNPc, L = Im, N-MeIm, py, 4-pic, 4-[formula omitted]Bupy, pip, THF, PPh₃) are studied. The ¹H NMR spectra of CoTNPc are found to be solvent dependent; the α- and β-proton signals of the phthalocyanine ring are very broad in DMSO-d₆ and benzene-d₆, and in chloroform-d₁ these signals are so broad that they could not be observed. Some irregular multiplicities in these proton NMR spectra result from the cobalt(II) complexes being mixtures of isomers. The isotropic shift vs.l/T Curie plot for (py)CoTNPc shows that the extrapolated isotropic shifts of the benzo-, methylene, and methyl protons on the phthalocyanine ring at infinite temperature are not zero, indicating there is a contribution from a dipolar interaction. For the axial ligands, the proton signals of the methyl groups of some ligands (L = N-MeIm, 4-pic, 4-[formula omitted]Bupy) are observed, and these signals are averaged by rapid chemical exchange between the free and coordinated ligands; the ligand aromatic proton signals of these ligands are not observed. However, the ²H NMR spectra, when L = pyridine-d₆, show that the ϒ-²H signal shifts in a direction different to signals from the α- and β-²H deuterons, suggesting a contact shift mechanism is dominant in this case. The ³¹P NMR spectra of in situ PPh₃/CoTNPc samples do not give any peaks, indicating that signals for the phosphine are extremely broad.
The elemental analyses, UV-visible spectra, IR, NMR, and ESR results suggest that CoTNPc and its five-coordinate species do not bind oxygen at the temperatures examined (77 K to ambient temperature).Science, Faculty of
Chemistry, Department of
Graduate
8
Moore, Charles H. M. "Coordination chemistry of guanidine derivatives". Thesis, University of Nottingham, 1987. http://eprints.nottingham.ac.uk/14354/.
Abstract (sommario):
This thesis describes an investigation of the coordination chemistry of l-cyanoguanidine (cnge), l-carbamoylguanidine (clge) and l-amidino-O-ethylurea (aOeu). Various copper(II) complexes of these analogous molecules were synthesised and characterised using mainly X-ray crystallographic and spectroscopic (infrared and UV-visible) techniques. Only bis (cnge) complexes were observed for copper(II) ions. The monodentate cnge ligands coordinated the copper(II) via their nitrile nitrogen atoms which were located in trans equatorial positions of the copper(II) ions's tetragonally distorted octahedral coordination sphere. Comparison of the infrared spectra of the complexes with that of cnge indicated that the spectra were highly diagnostic of coordination to the copper(II) ion. Clge exhibited amphoteric properties; the neutral, anionic and cationic derivatives formed complexes with the copper(II) ion. Whereas the former pair gave bis chelate complexes, the latter derivatives acted merely as a cation and was remote from the copper(II) ion's coordination sphere. Complexation of the neutral molecule resulted in a proton transfer from a terminal amine group to a central nitrogen atom permitting chelation via an imine nitrogen atom and a carbonyl oxygen atom to give a square planar CUN2O2 chromophore. The structural ramifications of this tautomeric shift were near identical to those observed upon cation formation which occurred by protonation of the central nitrogen atom of the uncoordinated neutral molecule. Unequivocal structural data could not be obtained for the complex of the anionic derivative. Spectroscopic analysis indicated, however, that chelation occurred via two imine nitrogen atoms to give a square planar CuN4 chromophore. Ethanolysis of cnge was effected in the presence of copper(II) ions and ethanol producing complexes of aOeu with a metal:ligand ratio of 1:1 or 1:2. In both complexes the ligand(s) chelated the copper(II) ion via two imine nitrogen atoms. The former complex, a dimer, exhibited a square pyramidal CUN2X3 chromophore (X=Cl,Br) whilst the latter complex was a bis chelate with a square planar CUN4 chromophore. Monitoring the Uv-visible and infrared spectra of ethanol solutions containing copper(II) chloride and cnge, indicated the presence of a plethora of reactions. However, it was concluded that initially mono and/or bis(cnge)copper(II) complexes, of low stability, were present in equilibrium with the reactants. Subsequently, ethanolysis of coordinated cnge occurred producing mono(aOeu)copper(II) complexes. Series first order kinetics approximated to those of the ethanolysis reaction. The ethanolysis process was then repeated to give the final product a bis(cnge)copper(II) complex.
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Grundy, Joanna. "Bifunctional amidines in coordination chemistry". Thesis, University of Sussex, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.398786.
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Mansfield, Natalie Emma. "Phosphaguanidines : coordination chemistry and catalysis". Thesis, University of Sussex, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.435610.
11
Aucott, Stephen Mark. "Coordination chemistry of aminophosphine ligands". Thesis, Loughborough University, 1999. https://dspace.lboro.ac.uk/2134/34492.
Abstract (sommario):
The reaction of [MCl2(cod)] (M = Pt, Pd) with two equivalents of 2-(diphenylphosphinoamino)pyridine, Ph2PNHpy, in warm acetonitrile led to cationic complexes of the type cis-[MCl(Ph2PNHpy-P,N){Ph2PNHpy-P}][Cl] (M = Pt, Pd) which exhibit broad single 31P{1H} NMR resonances due to their dynamic pyridyl exchange behaviour in solution. A single crystal X-ray diffraction study of the platinum species confirmed the proposed structure and revealed that adjacent complex molecules were held together by hydrogen bonding to the same chloride counter-ion. The bromo- and iodo-cis[MX(Ph2PNHpy-P,N){Ph2PNHpy-P}][X] (M = Pt, Pd; X = Br, I) complexes were obtained by metathesis from the corresponding chloride complex.
12
Cevik, Deniz. "Synthesis, purification, and characterization of tetraphosphine ligands". Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLX026/document.
Abstract (sommario):
L'évolution récente de la science écologique et durable nécessite des catalyseurs puissants, sophistiquées et dotés de propriétés spécifiques et accordables.Les catalyseurs bimétalliques qui contiennent deux ou plusieurs sites pour l'activation coopérative de substrats réagissant sur des centres métalliques voisins selon certaines conditions. Un certain nombre de squelettes, spécialement conçus pour générer des complexes exclusivement bimétalliques, ont été développés autour d'échafaudages de méthanodibenzodioxocine et de benzofurobenzofurane, y compris un certain nombre de ligands qui agissent comme donneurs de monophosphine dans deux centres métalliques différents. Ces ligands génèrent des espèces dinucléaires de manière fiable, mais les modes de coordination résultants sont imprévisibles.Ce travail de thèse présente la synthèse de ligands de tétraphosphine, dans lesquels des bras chélatants sont disponibles pour coordonner chacun des deux centres métalliques. La synthèse implique la préparation de 4,8-bis (sec-phosphines) de rac-6,12-méthano-12H-dibenzo [1,3] dioxocines et leur conversion en phosphines doublement chélatantes par l'élaboration de chaque fonctionnalité sec-phosphine en Les dérivés di (R) phosphinopropyle correspondants (R = Ph, Cy). Une étude de chimie de coordination préliminaire indique que l'environnement de coordination est fourni par ces ligands tétraphosphine binucléaires rigides. C’est ainsi que la préparation des complexes bimétalliques de PdII, PtII aurait été réalisé. Chacune des deux molécules de bras chélatants serait coordonnée à un métal. Enfin, des études préliminaires sur l'utilisation des ligands tétraphosphine comme supports pour la chimie de l'hydroformylation ont été réalisées. Les résultats actuels ne permettent pas encore d'établir définitivement un comportement coopératif entre les deux centres métalliques: Recent developments in green and sustainable science require more powerful, sophisticated and tunable catalysts. Bimetallic catalysts contain two or more sites for the activation of substrates and, under optimal circumstances, can allow cooperative activation of reacting substrates on neighboring metal centers. A number of backbones, designed specifically to generate exclusively bimetallic complexes have previously been developed around methanodibenzodioxocin and benzofurobenzofuran scaffolds, including a number of ligands that act as monophosphine donors to two different metal centers. These ligands generate dinuclear species reliably, but the resulting coordination modes are unpredictable. This work presents the synthesis of tetraphosphine ligands, wherein chelating arms are available to coordinate each of the two metal centers. The synthesis involves preparation of 4,8-bis(sec-phosphines) of rac- 6,12-methano-12H-dibenzo[l,3] dioxocins and their conversion into doubly chelating phosphines through the elaboration of each sec- phosphine functionality into the corresponding di(R)phosphinopropyl derivatives (R= Ph, Cy). A preliminary coordination chemistry study indicates that the tightly defined coordination environment provided by these rigid binucleating tetraphosphine ligands under study allowed bimetallic complexes of PdII, PtII to be prepared, in which each of the two chelating arms molecule coordinates to one metal. Finally outline studies on the use of the tetraphosphine ligands as supports for hydroformylation chemistry were performed. The current results do not yet allow cooperative behavior between the two metal centers to be definitively established
13
Fleischmann, Martin [Verfasser], e Manfred [Akademischer Betreuer] Scheer. "Oxidation and Coordination Chemistry of En Ligand Complexes under Weakly Coordinating Conditions / Martin Fleischmann ; Betreuer: Manfred Scheer". Regensburg : Universitätsbibliothek Regensburg, 2015. http://d-nb.info/1122354908/34.
14
Setyawati, Ika Agustin. "Coordination chemistry : basics to bioactive molecules". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0020/NQ46420.pdf.
15
Amantia, David. "Coordination chemistry of chelate-tethered nucleobases". Thesis, University of Newcastle Upon Tyne, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.417527.
16
Thompsett, Andrew Robert. "The coordination chemistry of unusual alkynes". Thesis, University of Warwick, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302650.
17
Wilson, Thomas Charles. "Coordination chemistry of the pentacyanocyclopentadienide anion". Thesis, University of Cambridge, 2014. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.708033.
18
Balaraman, Lakshmi. "COORDINATION CHEMISTRY OF N,N’- AZODOXIDES". Cleveland State University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=csu1556986156564604.
19
Farkas, Ildiko. "Coordination Chemistry of Actinide and Lanthanide Ions". Doctoral thesis, KTH, Chemistry, 2001. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3236.
20
Mjos, Katja Dralle. "Coordination chemistry of antimicrobial and anticancer agents". Thesis, University of British Columbia, 2015. http://hdl.handle.net/2429/54682.
Abstract (sommario):
The World Health Organization has named the resistance of microbes to known antimicrobial drugs as an increasingly serious threat to global public health. Isolates of the ESKAPE pathogens (E. faecium, S. aureus, K. pneumonia, A. baumanii, P. aeruginosa, and Enterobacter species) are responsible for many nosocomial infections each year that require complicated, and therefore expensive, medical treatment, often leading to death in immune-compromised patients. Over the past 50 years, (fluoro-)quinolone antimicrobial agents have been widely used in the clinic as broad-spectrum antibiotics, but lately growing resistance against this drug class has been reported. Combining metal ions with known organic small-molecule drugs is one strategy to overcome such developed resistances. Previously, the antimicrobial properties of copper(II) and gallium(III) had been investigated, leading to Greek mythology comparisons for their mechanism of action: Cu²⁺ as the ”Achilles Heel”, Ga³⁺ as the ”Trojan Horse” subterfuge for Fe³⁺. In this thesis, gallium(III) and copper(II) coordination complexes of (fluoro-)quinolone antimicrobial agents, and derivatives thereof, were synthesized in an attempt to combine the antimicrobial potency of Cu²⁺ and Ga³⁺ with that of the quinolone antimicrobial agents in one molecule. The antimicrobial susceptibility of these coordination complexes was evaluated against five isolates of the ESKAPE pathogens; combinational effects between the metals and the quinolone ligands were not observed. While the combination of metal ions with small, organic drug molecules may lead to novel potent metallodrugs, the interaction of metal ions with drugs in vivo is often associated with toxic side-effects of medical treatment, for which the iron(III)-mediated cumulative-dose cardiotoxicity of doxorubicin is one example. Vosaroxin is a first-in-class anticancer quinolone derivative in clinical trials. Unlike the anthracycline anticancer drug doxorubicin, vosaroxin is minimally metabolized in vivo. Spectrophotometric titrations and further studies of the isolated tris(vosaroxino)iron(III) and -gallium(III) complexes supported a strong coordination of the metal ion suggesting that vosaroxin treatment may not result in cardiotoxicity.Science, Faculty of
Chemistry, Department of
Graduate
21
Sishta, Chand. "The coordination chemistry of ruthenium porphyrin complexes". Thesis, University of British Columbia, 1990. http://hdl.handle.net/2429/30790.
Abstract (sommario):
This thesis work reports developments in the coordination chemistry of ruthenium porphyrin complexes, both in terms of the synthesis and chemistry of new compounds, as well as the study of the solution chemistry of some previously reported complexes. The synthesis, characterization and chemistry of ten new Ru(porp) coordination complexes in the oxidation states Ru[superscript]Ⅲ and Ru[superscript]Ⅳ containing halide (Br, CI) and other axial ligands (pyridine, CH₃CN, NH₃ and SbF₆) are described in this thesis. Some additional ten Ru(porp) complexes have been studied in situ.
Measurement of the rate constants for forward and reverse reactions and the corresponding equilibrium constant by 'H NMR and UV/visible spectroscopy for the dissociation of PPh₃ ligand from Ru(OEP)L(PPh₃) (OEP is the octaethylporphyrinato dianion; L = CO, PPh₃) in C₇D₈ to generate the previously reported five-coordinate Ru(OEP)L complexes allowed for an estimation of the Ru-P bond strength (64 ± 9 kJ mol⁻¹) in these complexes. A study of PPh₃ dissociation from Ru(OEP)CO(PPh₃) in C₇D₈ and in CDC1₃ indicates that solvation effects play a major role, with CDC1₃ being more capable than C₇D₈ of solvating the Ru(OEP)CO complex. The presence of trace H₂0 in these systems was a major problem, and the coordination of H₂0 to Ru(OEP)L complexes to generate the in situ Ru(OEP)L(H₂0) complexes (L = CO, PPh₃) is described. The formation of Ru(OEP)L(H₂0) and the observed difference in the solvation of Ru(OEP)CO by C₇H₈ and CHC1₃ indicate that truly Five-coordinate species may not exist in solution. The outer-sphere oxidation of Ru [superscript]Ⅳ(OEP)PPh₃ by 0₂ to give [Ru [superscript]Ⅳ(OEP)OH]₂0 was shown to occur only in the presence of H₂0.
Mechanistic studies on the previously reported reaction of HCI with [Ru(OEP)]₂ to generate Ru^(OEP)Cl₂ (C. Sishta, M.Sc.Thesis, University of British Columbia, 1986) show that solvent plays a major role in directing this oxidation reaction. A reaction stoichiometry of 4:1 between HCI and [Ru(OEP)]₂ in C₆D₆ or C₇D₈ showed that HCI itself was the oxidant and not trace Cl₂ in HCI, as thought previously. A range of HX acids having pK[subscript]a, values in the range 38 to less than -10 (HX = H₂, MeOH, H₂0, H₂S, CH₃COOH, C₆H₅COOH, HF, CF₃COOH, HN0₃, HBF₄, HCI. HBr, and HSbF₆) were tested for reactivity with [Ru(OEP)]₂in C₆D₆; the data showed that a strong acid (pK[subscript]a < ca. 0) was necessary to initiate reactivity. The complex Ru[superscript]Ⅳ(OEP)(SbF₆)₂ was generated in situ by reacting HSbF₆ with [Ru(OEP)]₂.
In CH₂C1₂, a 1:1 stoichiometric reaction between HCI and [Ru(OEP)]₂ was observed, instantly fanning a mixture of products, tentatively formulated as Rura(OEP)H and [Ru[superscript]Ⅲ(OEP)]₂CHCl₂ based on spectroscopic data. The species proved impossible to separate. These same products were formed slowly by the reaction of [Ru(OEP)]₂ with CH₂C1₂ in the absence of HCI, and kinetic studies suggest that a direct reaction of [Ru(OEP)]₂ with CH₂C1₂ is likely, rather than reaction of [Ru(OEP)]₂ with impurities in CH₂C1₂. The product mixture generated Ru(OEP)Cl₂ upon further reaction with HCI, both in the absence and in the presence of air. The complex Ru[superscript]Ⅳ(OEP)(BF₄)₂ was generated in situ by an analogous reaction of aqueous HBF₄ with the product mixture. The required hydrogen-containing co-product from the reaction of HX (X = Br, CI) with [Ru(OEP)|₂ in C₇D₈ or CH₂C1₂ was not detected, but was shown not to be H₂.
Oxidation of Ru(porp)(CH₃CN)₂ and Ru(OEP)py₂ (py = pyridine; porp = OEP, TMP (the dianion of tetramesitylporphyrin)) by gaseous HX (X = Br, CI) in the absence of air yielded Ru[superscript]Ⅳ(porp)X₂ complexes. The new compound Ru(TMP)Br₂ was synthesized by this method using the bis(acetonitrile) precursor, and was characterized by spectroscopy; the chloride analogue Ru(TMP)Cl₂ was generated in situ.
The magnetic properties (susceptibility and moment) of Ru(OEP)Br₂ from 6 to 300 K are unlike those reported for ruthenium(IV) non-porphyrin complexes, and reveal a significant contribution from temperature-independent paramagnetism.
The reaction of Ru(OEP)X₂ (X = Br, CI) with NH₃ gave the complexes Ru[superscript]Ⅲ(OEP)X(NH₃), which upon acidification under an inert atmosphere yielded the Rum(OEP)X compounds. These Ru111 complexes were characterized by spectroscopic techniques, and the solution chemistry of the five-coordinate species Ru(OEP)X was developed: the Ru[superscript]Ⅲ(OEP)X(CH₃CN) species were also characterized. Solvation of the five-coordinate species Ru(OEP)X (X = Br, CI) was observed in coordinating solvents to form the six-coordinate species Ru(OEP)X(solvent) (solvent = py, CH₃CN and MeOH). Estimates of the equilibrium constants for the association of these ligands to Ru(OEP)X were obtained from UV/visible titration experiments in CH₂C1₂. Similarly, the equilibrium constant for the association of Br to Ru(OEP)Br to generate in situ (n-Bu)₄N⁺[Ru[superscript]Ⅲ(OEP)Br⁺₂]", was measured. Disappointingly, the complexes Ru(OEP)X were shown not to catalyze the oxidation of organic substrates such as cyclohexene.
Electrochemical and spectroelectrochemical studies of the complexes Ru(OEP)X₂ and Ru(OEP)X (X = Br, CI) showed that the Ru[superscript]Ⅳ/Ru[superscript]Ⅲ couple occurred at 480-460 mV and 950-870 mV vs. NHE, respectively, and that the probable reductant for the reaction of Ru(OEP)X₂ with NH₃ was NH₃ itself. A facile reduction of Ru(OEP)(SbF₆)₂ gave the complex Ru[superscript]Ⅲ(OEP)SbF₆, by a probable homolysis of the Ru-F bond.
The outer-sphere oxidation of Ru(OEP)py₂ by air in the presence of HX acids gave the isolated or in situ characterized complexes [Ruin(OEP)py₂]+ X" (X = CI, Br, F, BF₄). Similar oxidation of Ru(OEP)(CH₃CN)₂ formed [Ru(OEP)(CH₃CN)₂]+ Br-. Electrochenucal studies showed that 0₂ in acidic media was capable of oxidizing the Ru(OEP)(solvent)₂ complexes (solvent = py, CH₃CN) to the Ru[superscript]Ⅲ complexes, presumably generating H0₂ .Science, Faculty of
Chemistry, Department of
Graduate
22
Farkas, Ildikó. "Coordination chemistry of actinide and lanthanide ions /". Stockholm, 2001. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3236.
23
Al-Rasbi, Nawal K. "The coordination chemistry of new multidentate ligands". Thesis, University of Sheffield, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.489370.
Abstract (sommario):
The content of this thesis is concerned with two distinctly independent areas of research: (i) the synthesis and coordination chemistry of new multidentate ligands and investigate their emission properties; (ii) the synthesis and study of new poly(pyrazol-1-yl)borate and Pt(II) based ligands and their lanthanide complexes.
24
Schleep, Mario [Verfasser], e Ingo [Akademischer Betreuer] Krossing. "Molecular and coordination chemistry of Tin(II)". Freiburg : Universität, 2017. http://d-nb.info/1143602927/34.
25
Metcalfe, John Edwin. "Studies in nickel and manganese coordination chemistry". Thesis, Queen's University Belfast, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263502.
26
Bishop, P. T. "The coordination chemistry of sterically hindered theolates". Thesis, University of Essex, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.381248.
27
Champness, Neil Robert. "Studies in ruthenium and osmium coordination chemistry". Thesis, University of Southampton, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239648.
28
Orchard, Simon David. "Synthesis and coordination chemistry of telluroether ligands". Thesis, University of Southampton, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.326303.
29
Mistry, Rakesh. "Synthesis and coordination chemistry of carboranyl phosphines". Thesis, University of Bristol, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.442207.
30
Khalaf, Majid Shannon. "Coordination chemistry of bicyclic guanidines and guanidinates". Thesis, University of Sussex, 2011. http://sro.sussex.ac.uk/id/eprint/7347/.
Abstract (sommario):
A [5:5] ligand based on the bicyclic guanidine 1,4,6-triazabicyclo[3.3.0]oct-4-ene [Htbo] has been synthesised. Two of these tbo units have been linked via a carbon bridgehead to form a novel bidentate ligand. Based on the knowledge that the electronic properties and specific steric interactions at a metal can lead to new insights into the relationship between crystal structure and ligand activity, the synthesised compounds have been investigated as polydentate ligands on the assumption that that they could be used to precisely control coordination environment. The corresponding [6:6] system which is based on the bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) [hppH] has also been synthesised and its coordination to silyl groups investigated. 1,4,6-triazabicyclo[3.3.0]oct-4-ene (Htbo) has been deprotonated to form the [tbo]- anion, which has been assessed as a ligand at Li, Al and Zn centres, allowing direct structural comparison to be made with the [hpp]- analogues. The coordination chemistry of Htbo and its derivatives has been explored through formation of a variety of transition metal complexes. Additionally, crystal structures showed that Htbo coordinates to the metal through the N-imine atom as a monodentate ligand to form trigonal planar, tetrahedral, square planar and octahedral complexes. The bis (tbo) methane H2C{tbo}2 ligand was found to support a range of coordination geometries and upon coordination, ionic structures such as [Pd(H2C{tbo}2)2][Cl]2 were formed. The synthesis of the monosubstituted compound hppSiCl3 afforded a series of (hpp) silanes which were isolated and reacted with LiOAr (Ar= 2,6-tBu2C6H3), providing a proof of N-Si bond stabilisation using a metal. Five examples of pentacoordinated silicon species have been synthesised via the reaction of [hpp]- and R2SiCl2 (R= Ph, Me).
31
Tatchell, Thomas. "Coordination chemistry of pendant aniline aza-macrocycles". Thesis, Cardiff University, 2005. http://orca.cf.ac.uk/56099/.
Abstract (sommario):
The selective functionalisation of triazamacrocycles is investigated herein, with the focus on 1, 4, 7-triazacyclononane (tacn) The ligands tris (5-fluoro, 2- aminophenyl) 1, 4, 7-triazacyclononane (L1), tris (4-fluoro, 2-aminophenyl) 1,4, 7- triazacyclononane (L") and tris (3-fluoro, 2-ammophenyl) 1, 4, 7-triazacyclononane (L ) were studied. X-Ray crystal data was obtained for (L,)M (C104)2.x:MeCN where M=Mn,,/FeII/Ni"/CuII/Znn/CdII/Hgn, (L2)M (C104)2 xMeCN where M=Mn1I/Fe,I/NiII/CuII/ZnII/Cdn and (L3)M (C104)2 xMeCN where M=Mn,1/NiI,/Cun/Zn,I/Cd,,/Pb11 complexes. The (L,)Cu (C104)2 complex exhibits a rare dynamic Jahn-Teller effect in the solid state. Selected compounds exhibit an interesting capping mode by their perchlorate counterions, with threefold-hydrogen bonding through the oxygen to the amine protons. The (L3)Pb (C104)2 crystal structure exhibits a typical geometry which accommodates a stereoactive lone pair from the lead centre. The variable temperature 'H NMR of tris 1, 4, 7-(2- aminophenyl) 1, 4, 7-triazacyclononane zinc bis tetraphenylborate was carried out over 298K-193K and spectra are included within. All complexes characterized by 'H NMR, 13C NMR, 19F NMR, IR, UV and where appropriate Mossbauer spectroscopy. The investigation into the synthesis and chemistry of the novel sulphonamide pentaazamacrocycles 1 -(/-tolylsulphonyl), bis 4, 7-(2-aminophenyl) - 1, 4, 7-triazacyclononane (L4), l-(/7-methoxyphenylsulphonyl), bis 4, 7-(2- aminophenyl) -1,4, 7-triazacyclononane (L5), l-(p-fluorophenylsulphonyl), bis 4, 7-(2-aminophenyl) -1,4, 7-triazacyclononane (L6) and 1-(2-mesitylsulphonyl) bis 4, 7-(2-aminophenyl) 1, 4, 7- tnazacyclononane (L7). The complexation with differing transition metals afforded the relevant complexes and X-Ray data was obtained for (L4)Ni/Zn/Cd.MeCN (C104)2.MeCN, (L4)Pb(C104) (C104).2(MeCN), 2 (L4)Cu (C104)4,4MeCN MeOH, (L5)Ni/Zn MeCN (C104)2.MeCN, and (L6)Ni MeCN (C104)2 MeCN H20. The (L4)Zn/Hg/Pb.MeCN (C104)2 MeCN, (L5)Zn/Hg MeCN (C104)2.MeCN, (L6)Zn MeCN (C104)2 MeCN and (L7)Zn MeCN (C104)2 MeCN compounds exhibit an unusual amine pattern in the 'H NMR. This was further studied by variable temperature *H NMR over the range of 298K-418K. The (L4)Cu(C104)2 crystal structure shows two complexes of the same compounds crystallizing in the same cell, each with slightly differing dimensions, but both of square based pyramidal geometry. The (L4)Pb(C104) C104.2.MeCN crystal structure exhibits a typical geometry which accommodates a stereoactive lone pair from the lead centre The bis sulphonamide l-(2-aminophenyl)-bis 4, 7-(/xira-tolylsulphonyl) 1, 4, 7- triazacyclononane (L8) was also prepared and its complexation of L8Ni/Cu/Zn/Cd coordination chemistry expanded. The fluorinated 7V-aryl tacn class was expanded by producing bis and tris ortho meta para-fluorinated phenyl ligands. This selective methodology led to the development of a tri substituted tacn ring with meta and /wra-fluorinated aromatic rings. We report the electronic spectroscopic examination of the autocatalytic oxidative degradation of the macrocyclic aniline moiety over 120hrs. The synthesis of mono l-(5-fluoro, 2-aminophenyl) bis 4, 7, (2-aminophenyl) 1, 4, 7- tnazacyclononane (L9), and mono l-(4-fluoro, 2-aminophenyl) bis 4, 7, (2- aminophenyl) 1, 4, 7-triazacyclononane (L10) are reported. The X-Ray single crystal data was collected for (L9)Mn/Zn (C104)2 The synthesis of 1, 4-bis-(2-amino, 4-fluorophenyl) homopiperizene (Ln) and its X-Ray crystal structure of (LnNi 2 MeCN)(C104)2 is described The conversion of N, N' bis (2-aminophenyl) 1, 4-diazacycloheptane by reaction with p- toluenesulphonyl chloride afforded N, AT bis (2-tosylaminophenyl) 1, 4- diazacycloheptane (Lu). Reaction with nickel perchlorate afforded the neutral complex (L')Ni . This dianionic ligand is proposed as a porphyrin analogue.
32
Cullen, William M. "Host-guest chemistry of polyhedral coordination cages". Thesis, University of Sheffield, 2015. http://etheses.whiterose.ac.uk/11545/.
Abstract (sommario):
Chapter 1 – Introduction Chapter 2 – Synthesis, characterisation and manipulation of a three component self-assembled system Chapter 3 – Development and utilisation of a fluorescence displacement assay for guest screening Chapter 4 – Prediction of guest binding using molecular docking Chapter 5 – The use of pH changes to control guest binding in water Chapter 6 – Highly efficient catalysis of the Kemp Elimination in the cage cavity.
33
Benson, Callum Giles Maxwell. "Synthesis and coordination chemistry of functionalised phosphazanes". Thesis, University of Cambridge, 2016. https://www.repository.cam.ac.uk/handle/1810/264415.
Abstract (sommario):
This thesis focuses on the chemistry of novel phosphazane species derived from the chloro-phosphazanes [ClP(μ-NR)]$_2$ and their use as ligands and building blocks for macrocyclic compounds. The introduction (Chapter 1) surveys previous literature in the area, which is pertinent to the new studies. One of the most important issues is the various ways in which dimeric phosph(III)azanes can be employed as precursors for new ligands and in the design of new types of inorganic macrocycles. In Chapter 2 the synthesis of new chloro-dimers of the type [ClP(μ-NR)]$_2$ is described, which are the primary starting materials. Chapter 3 concerns the substitution at the chlorine atoms of [ClP(μ-NR)]$_2$ by LiSH to give a variety of sulfur-containing PV species [S=P(H)(μ-NR)]$_2$. The thermodynamic preference for the cis or trans isomers of the latter are explored by detailed NMR spectroscopic and DFT calculation investigations. Deprotonation of the $^t$Bu derivative [S=P(H)(μ-N$^t$Bu)]$_2$ using organometallic bases (Chapter 3) led to the isolation of s-block salts (Mg$^2+$, Na$^+$, K$^+$) of the P$^III$ dianion [S-P(μ-N$^t$Bu)]$^2_2-$. The Mg$^2+$ salt was found to form a mononuclear complex in the solid state whereas the Na$^+$ salt formed a large cage comprising eight dianions and 16 Na$^+$ ions built around a NaSH core. These s-block metal salts were shown to be useful transfer reagents for the dianion towards complexation with main group metals (e.g., Sn and Ge). Chapter 4 explores the oxidation of the P$^III$ dianions [S-P(μ-N$^t$Bu)]$^2_2-$ by chalcogens to give the more stable P$^V$ species [(E=)P$^V$(-S)(μ-N$^t$Bu)]$^2_2-$ (E = S, Se). The increase in stability and lower reducing ability of the P$^V$ dianion allowed the formation of complexes with transition and main group metals. Reaction of [(E=)PS(μ-N$^t$Bu)]$^2_2-$ with chloro-dimers [ClP(μ-NR)]$_2$ led to the formation of homo- and heteroleptic P$^III$-P$^V$ phosphazane macrocycles of the type [{S=PV(μ-N$^t$Bu)}2(u-E){P$^III$(μ-NR)}$_2$]. These can be oxidised to give air- and moisture-stable all-P$^V$ species [{S=P$^V$(μ-N$^t$Bu)}$_2$(μ-E){S=P$^V$(μ-NR)}$_2$] by reaction with elemental sulfur. Finally, in Chapter 5 the substitution of the chlorine atoms in [ClP(μ-NR$^1$)]$_2$ by amines (R$^2$NH$_2$) is explored, to give a range of bis(amino) cyclophosphazanes [(R$^2$NH)P(-NR$^1$)]$_2$ containing chiral and non-chiral R$^2$ and R$^1$ groups. These species were used in the formation of early transition metal (Zr, Ti, Hf) complexes which are potential pre-catalysts for alkene polymerisation studies.
34
Hannon, Michael John. "Metal ion control in oligopyridine coordination chemistry". Thesis, University of Cambridge, 1993. https://www.repository.cam.ac.uk/handle/1810/272558.
35
Clifton, Jamie. "Phosphinothiophene ligands : coordination chemistry, catalysis, and polymerisation". Thesis, University of Bristol, 2016. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.687601.
36
Van, Veelen Arjen. "Uranium coordination chemistry in Mg-rich systems". Thesis, University of Manchester, 2014. https://www.research.manchester.ac.uk/portal/en/theses/uranium-coordination-chemistry-in-mgrich-systems(707b1576-699c-4f0a-b945-7482cfb7f51f).html.
Abstract (sommario):
In the UK, large quantities of intermediate level waste pose complex radiological remediation challenges. Chemical understanding of uranium in these Mg-rich sludges is vital. Previous studies have examined uranium uptake by calcium carbonate minerals (calcite and aragonite) under conditions pertinent to both natural and anthropogenically perturbed systems. However, research on uranyl uptake by magnesium-rich minerals such as magnesite [MgCO3], brucite [Mg(OH)2], nesquehonite [MgCO3·3H2O] and hydromagnesite-[Mg5(CO3)4(OH)2·4H2O] has not, to the best of our knowledge, been previously conducted. Such experiments will improve our understanding of the mobility of uranium and other actinides in natural lithologies such as dolomitic limestones or mafic igneous emplacements, as well as provide key information applicable to nuclear waste repository strategies involving Mg-rich phases. By two EXAFS techniques, we determined: (1) where uranyl (UO22+) is adsorbed, and (2) how uranyl is attached to the mineral surface. Therefore powder experiments of U(VI) were performed with magnesite, brucite, nesquehonite and hydromagnesite. The second experiment (GIXAFS) consisted of single crystals of magnesite (10.4) and brucite (0001). The powders were reacted in solution pH ~8.5 with U(VI)nitrate for 48 hrs. under ambient PCO2 = -3.5. The single crystals were reacted under ambient and reduced PCO2 ~ -4.5 for 48 hrs. with concentrations of U(VI)chlroride above (500; 50 ppm) and below (5 ppm) solubility of schoepite [UO2(OH)2·H2O]. The GIXAFS measurements were made at χ = 0˚ and χ = 90˚ relative to the synchrotron beam polarisation to uequivocally determine the adsorbate structures. Kd values for Mg-carbonate phases were comparable to or exceeded those published for calcium carbonates. GIXAFS results clearly showed polarisation for both ambient and reduced PCO2. XANES results showed uranyl is oriented with the axial oxygens perpendicular to the mineral surface. This implies, using also X-ray reflectivity and diffuse scatter, local hydrated bayleyite [Mg2(UO2)(CO3)3∙18H2O] and possible rutherfordine-like [UO2CO3] regions, which will be useful to predict uranium behaviour in various remediation processes.
37
Youfu, Katsuyuki. "Coordination chemistry and reactivities of expanded porphyrins". 京都大学 (Kyoto University), 2006. http://hdl.handle.net/2433/144223.
38
Clayton, Hayley J. "Synthesis and coordination chemistry of ligands for supramolecular chemistry and sensing applications". Thesis, University of Huddersfield, 2008. http://eprints.hud.ac.uk/id/eprint/6954/.
Abstract (sommario):
A series of multidentate N-donor ligands have been synthesised all containing pyridyl and pyridyl/thiazole units and their coordination behaviour is described. The ligands are classified into four types; i) terpyridine containing pyridyl/thiazole ligands (L1-3); ii) pyridyl/thiazole ligands containing a 3,3′-disubstituted bipyridine core. (L4-8); iii) 2,2′-bipyridine containing a crown ether moiety (L9-11); and iv) a 2,2′- bipyridine derived ligand containing a urea functional group in the 3,3′-positions (L12). Chapter II describes terpyridyl/pyridyl/thiazole ligands: - the synthesis of (L1-3) is described and the complexes ([Cu(L1)][ClO4]2, [Ni(L2)][ClO4]2, [Co(L2)][ClO4]2, [Cd3(L3)2][ClO4]6) structurally characterised. Partitioning of the ligands (L1-3) is dependant on the position of the thiazole ring within the ligand chain. This partitioning is found to occur at a position adjacent to that of the thiazole ring in all but the L2 ligand complexes, where it is partitioned preferentially at a position creating favourable coordination geometry for the metal ion. Chapter III describes 3,3′-disubstituted pyridyl/thiazole ligands (L4-8): - the novel potentially hexadentate ligands (L4, 5), the potentially octadentate ligand (L6) and the potentially tetradentate ligands (L7, 8) have been synthesized and structurally characterised. All ligands are found to partition at the central pyridine unit due to unfavourable steric interactions to form a pyridyl/thiazole/pyridyl-binding domain (L4-6) and the pyridyl/thiazole-binding domain (L7,8). The substituents are found to dominate the control of the formation of complexes produced ([Zn(L4)][ClO4]2, [Cd(L5)][ClO4]2, [Cd2(L6)2][ClO4]2, [Cd2(L8)2][ClO4]2). Chapter IV, Section 1 describes ditopic bipyridine/crown ether ligands: - the synthesis of (L9-11) is described and the Ru (II) complexes (L9-11) structurally characterised. The Ru(II) complexes of these 3,3′-disubstituted crown ether species were found to luminesce. Modulation of the luminescent properties of the ruthenium complex was investigated with a selection of common cations but resulted in little or no response. Chapter IV: - Section 2- Ditopic bipyridine/urea ligands: - the novel ligand containing urea substituent side chains (L12) has been synthesised and a ligand containing both pyridine and urea substituents has been synthesised and characterised. A ruthenium complex (X) was synthesised with ligand (L12) and (bipy)2RuCl2, the resulting structure confirmed via 1H & 13C NMR as well as electrospray mass spectrometry (ESI-MS). Unfortunately no complexes have been structurally characterised due to the instability and decomposition of the complex after a short period of time. The ruthenium complex however was found to luminesce; ligand/anion recognition studies with complex (X) and a selection of common anions showed a marked change, a ten fold increase in the luminescence was observed with the addition of H2PO4 - when in a non-aqueous solvent.
39
Fischbach, Urs Christian. "Rigid phosphane-olefin ligands : synthesis and coordination chemistry /". Zürich : ETH, 2006. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=16733.
40
Uppal, Baljinder S. "'Click' chemistry in coordination and supramolecular chemical applications". Thesis, University of Huddersfield, 2012. http://eprints.hud.ac.uk/id/eprint/18043/.
Abstract (sommario):
The term “click chemistry” was first coined by Sharpless and co-workers in 2001 and encompasses a range of high yielding organic coupling reactions which are rapid, highly selective and proceed with good functional group tolerance. Furthermore the reaction conditions are mild and require minimal workup and product purification. The most prominent example of these reactions is the copper catalysed alkyne/azide cycloaddition (CuAAC) for the formation of 1,4- disubstituted-1,2,3-triazoles. CuACC has been utilised in a variety of chemical disciplines including organic synthesis, the modification of biological macromolecules and in polymer and materials chemistry. More recently this reaction has shown a growing interest from the inorganic community for the design of new ligands for transition metal complexes and their supramolecular assemblies. In this thesis, I present my results on the use of the 'click' chemistry in coordination and supramolecular chemical applications. Described in chapter 3 is the synthesis of 1,4 disubstituted-1,2,3-triazole ligands which can act as either axial monodentate ligands, through the N3 atom of the triazole ring, or as bidentate N^N donor ligands if a pyridyl substituent is incorporated into a chelate ligand framework. The photophysical effects of these ligands were investigated on rhenium tricarbonyl complexes. It was found that replacing the Cl- ligand by the triazole stabilises the energy of the HOMO with respect to the LUMO and results in a blue shift of the emission maximum whilst changing the bidentate ligand by replacing the bipyridyl ligand by pyridinetriazole ligand elevates the LUMO with respect to the HOMO again resulting in a blue shift in luminescence. Described in chater 4 is the synthesis of 4-azido-2,2’-bipyridyl and 4,4’-diazido-2,2’-bipyridyl ligands and the CuAAC modification thereof. 4-azido-2,2’- bipyridyl was incorporated in to [Ru(p-cymene)( 4-azido-2,2’-bipyridyl)Cl]+ type complexes. The CuAAC reaction was utilised to hemically modify the periphery of a metal complex hen an azido substituted ligand is allowed to react with a range of alkynes. Through this approach a second metal binding domain can easily be introduced upon reaction with 2-pyridyl acetylene. [Ru(p-cymene)( 4-azido-2,2’-bipyridyl)Cl]+ and “click” chemistry can be used as a potential tool in building metallo-supramolecular species. We have therefore made some of the first steps towards the goal of the development of a general “click” chemistry-based methodology for the construction of functional supramolecular architectures via azide-functionalised transition metal complexes. Desciribed in chapter 5 is the preperation of 1,2,3-triazole bridged luminescent redox switches. Ruthenium, iridium and rhenium complexes incorporating ferrocenyl-bipyridyl ligand in which the ferrocene unit is tethered to the bipyridyl through a 1,2,3-triazole linkage were prepared. We have developed two potential luminescent switches with ferrocene tagged bipyridyl ligands containing a CuAAC derived triazole linker. The ferrocene moiety quenches the Ru/Ir based luminescent emission, presumably by electron transfer across the triazole bridge. We have demonstrated that the luminescent emission can be switched on by oxidation of the Fc moiety to Fc+. Described in chapter 6 is the synthesis and characterisation of a range of ligands, incorporating the 1,2,3-triazole moiety, which have designed to act as bridging ligands for the construction of supramolecular assemblies. We have subsequently prepared two dinuclear ruthenium and iridium complexes of the 4-pyridyl-1-(2,2’-bipyrid-4-yl)-1,2,3-triazole bridging ligand, and carried photophysical studies. We have shown that the dinuclear species exhibit greater luminescent intensities than mono-nuclear model complexes because the metal centre coordinated to the pyridine-triazole domain acts as a sensitizer for the metal centre coordinated to the bipyridyl domain through a photoinduced energy transfer mechanism. This shows that there is efficient transfer across the bridging ligand.
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Szymczak, Nathaniel Kolnik. "Coordination chemistry of dihydrogen and dihydrogen hydrogen-bonding /". view abstract or download file of text, 2007. http://proquest.umi.com/pqdweb?did=1400962351&sid=1&Fmt=2&clientId=11238&RQT=309&VName=PQD.
Abstract (sommario):
Thesis (Ph. D.)--University of Oregon, 2007.Typescript. Includes vita and abstract. Includes bibliographical references (leaves 307-324). Also available for download via the World Wide Web; free to University of Oregon users.
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Babecki, Ryszard. "Aspects of the coordination chemistry of betaketophosphoryl compounds". Thesis, Staffordshire University, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.278915.
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White, David James. "The coordination chemistry of some multidentate thioether ligands". Thesis, University of Oxford, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239238.
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Rawle, Simon Charles. "The coordination chemistry of some multidentate thioether ligands". Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.329963.
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Lippolis, Vito. "Studies on the coordination chemistry of macrocyclic ligands". Thesis, University of Nottingham, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311755.
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Baysal, Akin. "Coordination chemistry of molecules derived from 1,10-diazaphenanthrene". Thesis, University of Kent, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.362310.
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Martin, Nicola Catherine. "Supramolecular coordination chemistry of mellitic and pyromellitic acids". Thesis, University of Newcastle Upon Tyne, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.412650.
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Russo, Luca. "Supramolecular coordination chemistry of isophthalic and trimellitic acids". Thesis, University of Newcastle Upon Tyne, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.427315.
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Oldroyd, Richard Duncan. "The coordination chemistry of periodate and tellurate ligands". Thesis, University of Southampton, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.240580.
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Akpan, C. A. "Coordination chemistry of phospha-allenes and phospha-alkenes". Thesis, University of Sussex, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375131.