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Thematische Bibliographien / Metal complexes / Dissertationen

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Dissertationen zum Thema „Metal complexes“

Autor: Grafiati

Veröffentlicht am 4. Juni 2021

Zuletzt aktualisiert am 31. Juli 2024

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1

Brayshaw, Simon Keith. „Metal complexes bearing pendant alkynes and metal complexes of N-heterocyclic carbenes“. University of Western Australia. School of Biomedical and Chemical Sciences, 2004. http://theses.library.uwa.edu.au/adt-WU2005.0017.

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This thesis is comprised of two parts. The first part describes the synthesis of cyclopentadienyltungsten complexes containing a pendant alkyne group (I), and the subsequent photo-induced intramolecular coordination of the alkyne, forming complexes such as II. Compounds containing intramolecularly coordinated alkynes are rare, and this is the first example using cyclopentadiene as the core ligand. The second part describes the synthesis and structural characterisation of a number of novel metal complexes containing N-heterocyclic carbene ligands, some containing particular functionality for taylored applications. New methods were used to form complexes of rhodium, iridium, silver and gold (eg. III, IV). Structural and spectroscopic properties of the complexes were correlated with electronic characteristics of the ancillary ligands. A number of rhodium and iridium complexes (eg. IV) derived from imidazolium-linked cyclophanes were synthesised and structurally characterised. Complexes of N-heterocyclic carbenes with pendant ionic groups were synthesised, and a preliminary examination of their catalytic activity in water was performed. N-Heterocyclic carbenes complexes containing an electron withdrawing nitro group were synthesised and the effect of the nitro group on metal-ligand bonding was examined.

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2

Barron, Andrew Ross. „Transition metal aluminohydride complexes“. Thesis, Imperial College London, 1986. http://hdl.handle.net/10044/1/37935.

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3

Alem, Nassreen. „Zeolite encapsulated metal complexes“. Thesis, University of Reading, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239055.

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4

Jasim, Naseralla. „Transition metal bifluoride complexes“. Thesis, University of York, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.323538.

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5

Ho, Kin-ying. „Synthesis, characterization and spectroscopic properties of d6 and d10 metal complexes with pyridyl amine ligands /“. Hong Kong : University of Hong Kong, 1999. http://sunzi.lib.hku.hk/hkuto/record.jsp?B20667905.

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6

Jones, Simon C. „Metal-metal coupling in bi- and multimetallic systems : organometallic pentalene and group 14-bridged cyclopentadienyl complexes of transition metals“. Thesis, University of Oxford, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.270635.

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7

Humphrey, Elizabeth Rebecca. „Tris(pyrazolyl)borate metal complexes : new ligands and metal-metal interactions“. Thesis, University of Bristol, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.340301.

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8

Zhao, Ningfeng Eichhorn David M. „Cyano-substituted polypyrazolylborate metal complexes“. Diss., Click here for available full-text of this thesis, 2005. http://library.wichita.edu/digitallibrary/etd/2005/d019.pdf.

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Thesis (Ph.D.)--Wichita State University, College of Liberal Arts and Sciences, Dept. of Chemistry.
"December 2005." Title from PDF title page (viewed on February 8, 2007). Thesis adviser: David Eichhorn. Includes bibliographic references (leaves 123-128).

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9

Rao, Sumitrananda N. R. „Novel adsorbents using metal complexes“. Thesis, Georgia Institute of Technology, 1993. http://hdl.handle.net/1853/10200.

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10

Felsher, Dave. „Electrowinning of metal - DETA complexes“. Thesis, McGill University, 2000. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=33329.

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Sludges formed by lime treatment of acidic mine effluents are a widespread environmental hazard. One treatment option is to recover the toxic and potentially valuable contained metals. A method has been reported to selectively recover the metals by leaching with a complexing agent, diethylenetriamine (DETA). In this thesis a novel method has been developed to recover metals from the metal---DETA complexes by direct electrowinning. Copper was studied initially as a test system due to the relative ease with which it is recovered in conventional sulphate electrowinning. The main industrial interest, and hence the main focus of the work, is in the nickel---DETA system. For both metals, initially batch tests were run to determine acceptable electrowinning conditions. These were followed by recycle tests to simulate a potential process flowsheet. In the nickel-DETA system the effects of pH, nickel concentration, temperature, and DETA to nickel ratio on current efficiency were determined.
Recycle tests for copper showed that a steady DETA concentration was achieved after ca. six hours. In the case of nickel, the system seemed to continually deteriorate. A pH range of 4.6 to 4.8 maximized the current efficiency, due to a competition between hydrogen formation at low pH and increased complex stability at high pH. Both increasing Ni concentration and temperature increased the current efficiency, while increasing the DETA to nickel ratio lowered it.

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11

Tovilla, Cao-Romero Jorge Alberto Francisco. „Molecular recognition with metal complexes“. Thesis, Imperial College London, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.436343.

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12

Harrison, Simon. „Metal-arene complexes and clusters“. Thesis, University of Nottingham, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.280332.

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13

Jones, P. „Studies of chiral metal complexes“. Thesis, Bucks New University, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.373593.

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14

Blackwell, Elizabeth Sarah. „Fluxionality in organonitrogen metal complexes“. Thesis, University of Exeter, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.332328.

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15

Harrison, Stephen Anthony. „Novel chiral cyclopentadienyl metal complexes“. Thesis, University of Southampton, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.442873.

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16

Veighy, Clifford Robert. „Novel cyclopentadienyl transition metal complexes“. Thesis, University of Southampton, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.327366.

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17

Zard, P. W. „Transition metal complexes with pyrimidinethiones“. Thesis, Imperial College London, 1988. http://hdl.handle.net/10044/1/47322.

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18

Miles, Philip James. „Metal complexes for cancer chemotherapy“. Thesis, University of Manchester, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.627992.

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19

Jones, Michael David. „Trimethylenemethane and oxodimethylenemethane metal complexes“. Thesis, University of Leicester, 1986. http://hdl.handle.net/2381/33764.

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Chapter 1 reviews the literature concerning trimethylenemethane and oxodimethylenemethane metal complexes and their r?le in organic synthesis. The preparation and characterisation of ?4-trimethylenemethane metal complexes of iridium, rhodium, osmium and ruthenium are presented in Chapter 2, together with the molecular structure of three of these complexes which establishes the presence of the ?4-trimethylenemethane ligand. The room temperature 1H n.m.r. spectra show the expected features for a static structure and no sign of rotation of the trimethylenemethane ligand was observed at higher temperatures. Preliminary investigation into the reactivity of these trimethylenemethane complexes is detailed in Chapter 3. A series of cationic ?4-trimethylenemethane complexes are prepared by the reaction of [Ir{?4-C(CH2)3}C1 (CO)(PPh3)] with silver hexafluorophosphate in the presence of a donor ligand such as carbon monoxide or ethene. The reactions of these cationic complexes with neutral and anionic nucleophiles are investigated and show that displacement of other donor ligands or attack on co-ordinated carbonyl and ethene ligands occurs, rather than attack at, or displacement of the trimethylenemethane ligand. Chapter 4 describes the reaction of 3-trimethylsilyl-2-(methyl- sulphonyloxymethyl) prop-l-ene with d10-metal complexes of platinum, palladium and nickel. The isolation of ?3-2-trimethylsilylmethylallyl palladium and platinum complexes are of interest since they are postulated intermediates implicated in the generation of the catalytic species [Pd (?3-trimethylenemethane) (PPh3)2]. The d10 -nickel complex [Ni{P(OEt)3}4] catalyses the cycloaddition of trimethylenemethane to electron-deficient alkenes and imines, the latter reaction affords a high yield synthesis of 4-methylenepyrrolidines. The final Chapter describes the reactions of 3-chloro-l-(trimethyl-silyl)propan-2-one and 3-chloro-2-(trimethylsiloxy)prop-l-ene with low-valent metal complexes to afford oxodimethylenemethane complexes of platinum, iridium, and osmium. The molecular structure of two of these complexes establishes the presence of an ?3-oxodimethylenemethane ligand. The silylenol ether, 3-chloro-2-(trimethylsiloxy)prop-l-ene was readily prepared from 3-chloro-l-(trimethylsilyl)propan-2-one, the isomerisation being catalysed by a number of low-valent metal complexes.

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20

Greig, John A. „Studies on metal macrocyclic complexes“. Thesis, University of Edinburgh, 1991. http://hdl.handle.net/1842/13953.

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21

Johnson, Donald Martin. „Cyanoscorpionates and Transition Metal Complexes“. Digital Commons @ East Tennessee State University, 2010. https://dc.etsu.edu/etd/1725.

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The new dihydrobis(4-cyano-3-tert-butylpyrazolylborate) ligand has been synthesized. Isolated crystals of the thallium complex were collected and structurally characterized by X-ray diffraction. Transition metal complexes of the ligand are currently under investigation.

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22

VALLETTA, ELISA. „Metal complexes with biological activity“. Doctoral thesis, Università degli Studi di Cagliari, 2016. http://hdl.handle.net/11584/266768.

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Cancer is a group a diseases that involves abnormal cell growth with potential to invade or spread to other parts of the body, and it represents the second leading cause of death in developed countries. Cisplatin is one of the most chemotherapeutic drug. In spite of its great efficacy, it shows several side effects and most patients develop a resistance to cisplatin. To overcome the cisplatin resistance, drugs are often administered in combination in order to exploit the drug synergy. After discovery of cisplatin, the research focused on metal complexes less toxic, more effective and that exploit synergistic effect when used in combination. In this work I studied new copper, zinc and vanadium complexes with biological activity. I tested in vitro the studied compounds alone and in combination with drug currently in use against a panel of wild type tumour cell lines and their cisplatin-resistant sublines. I applied chemometric tools such as experimental design (ED) and artificial neural networks (ANNs) to the biochemical data collected. Finally, I used the artificial neural networks to evaluate the cell culture cross-contamination. I selected a new family of copper(II) complexes with 1,10-phenanthroline (phen), 1,10-phenanthrolin-5,6-dione (phendione), and 1,10-phenanthrolin-5,6-diol (phendiol) for the synthesis of new antiproliferative agents. Considering that the DNA is an important target for several cytotoxic metal complexes, I studied the interaction of these Cu(II) complexes with DNA. I tested the ligands and complexes against normal and tumour derived human cell lines. I tested combinations of the studied complexes and cisplatin for their potential synergistic effect against a panel of wild type tumour cell lines and their cisplatin-resistant sublines. I evaluated the selectivity of drug combinations testing the compounds also against ex vivo cultures of human normal cell lines. Considering that the synergy may arise from a chemical reaction among the drugs, I studied the possible formation of new adducts between cisplatin, copper(II) complexes and glutathione. I studied the phospholipid profile of wild type human cancer cell lines and their cisplatin-resistant sublines, given that changes in lipid composition and distribution on the cell membranes have been observed in cancer cells. The in vitro cultured cell lines are widely used as model in biomedical research and the cross-contamination of cell lines represents a highly relevant problem. The ex-post discovery of erroneous results and conclusions led to paper retraction and many high-impact journals started to adopt a zero-tolerance policy requiring confirmation of cell line identity as prerequisite for publication. On the base of these considerations, I decided to develop and validate a method for evaluation of cell culture cross-contamination. I also studied zinc and vanadium complexes. Zinc is an essential metal ion involved in a wide variety of biological processes and several proteins bind zinc for their proper functioning. I studied zinc complexes with the drug methimazole (MeImHS) and its anion (MeImS) in order to provide information for the structure prediction and reactivity of Zn-metalloproteins and -metalloenzymes. Vanadium plays a number of roles in biological systems and vanadocene dichloride was the first discovered vanadium species with antitumour activity. Considering that the mechanism of the anticancer agent vanadocene dichloride is closely related to the biotransformation in the blood plasma, I studied the speciation of vanadocene dichloride in the plasma under physiological conditions. In order to prepare new metal complexes, I also synthesized and characterized a new group of Schiff base ligands derived from salicyladehyde and six natural amino acids. For the analysis of the collected data, I used the ED to set up the experiments for the evaluation of the synergistic effect of drug combinations, and for the study of the possible formation of new adducts between cisplatin, glutathione and studied complexes. I used ANNs for predict and quantify the synergism of drugs, and for the evaluation of cell culture cross-contamination levels.

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23

Rais, Daniela. „Supramolecular chemistry of metal anynyl and metal phenanthroline complexes“. Thesis, Imperial College London, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.271988.

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24

Plowright, Richard J. „Spectroscopy and interactions of metal and metal cation complexes“. Thesis, University of Nottingham, 2010. http://eprints.nottingham.ac.uk/11448/.

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The work in this thesis looks at the spectroscopy and interactions of metals and metal cation complexes. There are two aspects of this vast subject that are considered: the electronic spectroscopy of Au-RG complexes and the ion-molecule chemistry of metals important in the mesosphere-lower thermosphere (MLT) region of the atmosphere. The spectroscopy of the molecular states in the vicinity of the strong Au 2P3/2, 1/2 ← 2S1/2 atomic transition, have been studied for the Au-RG (RG = Ne, Ar, Kr, Xe) series using resonance enhanced multiphoton ionization (REMPI). The spectroscopy of these systems was more involved than expected and high level ab initio calculations were required to complement and aid interpretation of the REMPI spectra obtained. Two main effects were seen to influence the spectroscopy in this energetic region — the mixing between D2Π1/2 and E2Σ1/2+ states through spin-orbit interactions and the interaction of lower lying states arising from the Au(2D) + RG (1S0) asymptote, resulting in predissociation being observed. The MLT is the only region of the Earth’s atmosphere in which metals exist in a free atomic state. It is known that their presence in this region occurs via the ablation of meteors entering the upper atmosphere, but certain aspects of their chemistry are still unclear. Using high level ab initio theory, spectroscopic constants were determined for metal cation complexes that can be formed in this region. These values are used by collaborators in conjunction with laboratory measurement to establish accurate rate coefficients that will allow the ion-molecule chemistry of calcium and magnesium in the MLT region to be modelled.

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25

Bradley, Patricia Marie. „Photochemistry and photophysical properties of metal-metal dimer complexes /“. The Ohio State University, 2002. http://rave.ohiolink.edu/etdc/view?acc_num=osu1486461246814571.

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26

何建英 und Kin-ying Ho. „Synthesis, characterization and spectroscopic properties of d6 and d10metal complexes with pyridyl amine ligands“. Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1999. http://hub.hku.hk/bib/B31220885.

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27

Chan, Hoi-shan. „Syntheses, reactivity and coordination chemistry of d10 metal complexes of phosphorus and nitrogen donating polydentate ligands /“. Hong Kong : University of Hong Kong, 1999. http://sunzi.lib.hku.hk/hkuto/record.jsp?B2079289X.

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28

Chamayou, Anne-Christine [Verfasser], und Christoph [Akademischer Betreuer] Janiak. „Chiral metal-Schiff base complexes = Chirale Metal-Schiff-Base-Komplexe“. Freiburg : Universität, 2011. http://d-nb.info/1115490567/34.

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29

Barthram, Anita Marie. „Metal-metal interactions in polynuclear complexes of ruthenium and osmium“. Thesis, University of Bristol, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.326683.

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30

Ziehm, Christopher Joseph. „ENHANCEMENT OF ELECTRONIC COUPLING IN METAL-METAL QUADRUPLY BONDED COMPLEXES“. The Ohio State University, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=osu1416315259.

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31

Young, George Hansen. „Reactions of transition-metal propargyl complexes with polynuclear metal carbonyls /“. The Ohio State University, 1989. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487672631602474.

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32

Lam, Chong Ho. „Metal complexes containing oxygen tripod ligands : models of metal oxides /“. View Abstract or Full-Text, 2003. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202003%20LAMC.

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Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003.
Includes bibliographical references (leaves 275-290). Also available in electronic version. Access restricted to campus users.

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33

Iskra, Andreas. „Photofragmentation studies of metal ion-molecule complexes and metal oxides“. Thesis, University of Oxford, 2017. https://ora.ox.ac.uk/objects/uuid:d3663b37-7954-47a3-83e3-4a9ad7b9e3e7.

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Gas phase metal-containing complexes provide suitable systems in which to study fundamental binding motifs between a metal ion and molecules in the absence of any solvent, support or competing charge effects. In this thesis, metal-containing species are explored experimentally using infrared resonance enhanced photodissociation (IR-REPD) spectroscopy and velocity map imaging (VMI). The experimental results are further interpreted with the aid of spectral simulations based on density functional theory (DFT). These are the first studies reported using a newly built IR-REPD spectrometer equipped with a purpose-built laser ablation source to allow for the study of single metal ion-molecule complexes. The laser ablation source is shown to efficiently produce various complexes including Rh⁺(CO₂)_n, VO₂⁺(N₂O)_n and Au⁺(CH₄)_n and the IR-REPD spectrometer has been characterised against a well-studied system of V⁺(CO₂)_n complexes. In order to record the IR-REPD spectra for small metal ion-molecule complexes, an argon atom is employed as the inert messenger. A combined IR-REPD spectroscopy and DFT investigation of M⁺(CO₂)_n complexes (where M = Co⁺, Rh⁺ and Ir⁺) reveals a common [M⁺(CO₂)₂] core structure for all three considered metal ions. Additional ligands, which are not directly bound to the central metal ion, experience lower perturbation as evident in the reduced blue-shift for the ligand in the outer coordination shells. A further IR-REPD/DFT study involving CO₂ complexation around NbO₂⁺ and TaO₂⁺ ions reveals a strongly-bound core of four CO₂ ligands around the MO₂⁺ ion (M = Nb, Ta). A significant increase in the intermolecular bond distances for the second coordination sphere ligands coincides with a decrease in the calculated binding energies. Velocity map imaging is employed to explore the rich photodissociation dynamics of VO in the vicinity of C⁴Î£- - X⁴Î£-(v',0) vibronic transitions in VO. The final quantum state distribution was observed to be strongly dependent on the intermediate vibronic state of VO via which the dissociation threshold is reached. This work provides a refined value for the VO dissociation energy of D₀(VO) = 53190 ± 261 cm^-1 in excellent agreement with available literature.

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34

Holder, Alan John. „Studies on transition metal macrocyclic complexes“. Thesis, University of Edinburgh, 1987. http://hdl.handle.net/1842/10961.

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35

Onyiriuka, Emmanuel C. „Pyrazolyl ligands in mixed metal complexes“. Thesis, University of British Columbia, 1986. http://hdl.handle.net/2429/27178.

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The anions LMo(CO)₃⁻ (L = MeGapz₃ or MeGa(3,5-Me₂pz)₃) have been isolated as the Na⁺, Et₄N⁺ or HAsPh₃⁺ salts and the solution structures of the Na⁺ salts in THF have been defined by analysis of the v[sub CO] ir spectra. Ion-pair interaction of the LMo(CO)₃⁻ anion with Na⁺cation in THF solution is apparent from the spectroscopic evidence obtained. The MeGapz₃Mo(CO)₃ ⁻anion reacted with HCl or EtBr to give the seven-coordinate [MeGapz₃]-Mo(CO)₃R (R = H or Et) complexes. However, with Mel or PhCOCl complexes of the type [MeGapz₃]Mo(CO)₂(n₂-COR) (R = Me or Ph) were obtained. The reactions of the LMo(CO)₃⁻ ions (L = MeGapz₃ HBpz₃ or Me₂Gapz(0-CH₂CH₂NMe₂)) with a variety of transition metal halide species have yielded complexes with transition metal-transition metal bonds. The X-ray crystal structures of two such complexes [MeGapz₃]Mo(CO)₃Cu(PPh₃) and [MeGapz₃]Mo-(CO)₃Rh(PPh₃)₂ have been determined. The former complex provides a rare example of a 3:3:1, or capped octahedral structure, with a short (mean) Mo-Cu distance of 2.513(9)Å. The latter compound displays one terminal and two bridging CO ligands and a Mo-Rh distance of 2.6066(5)Å. Transition metal-group 14 (Si, Ge or Sn) element bonded complexes of the type [MeGapz₃]Mo(CO) ₃M'Y (Y = Me₃ or Ph₃, M' = Ge or Sn; Y = Me₃, M' = Si; Y = Me₂Cl, M' = Sn) have been prepared from the reaction of the MeGapz₃Mo(CO)₃anion with the appropriate organo-group 14 chloride. In all the complexes, direct Mo-M' (M' = Si, Ge or Sn) single bonds are featured. The [MeGapz₃]Mo(CO) ₃SnMe₂Cl complex shows an interesting solution behaviour in which a transition from a 3:4, or piano stool structure, to a 3:3:1, or capped octahedral arrangement, is thought to occur. The 3:3:1 structure has been demonstrated in the solid state for the [MeGapz₃]Mo(CO)₃SnPh₃ compound by means of a crystal structure determination. The 'Mo-SnPh₃' and the 'Mo-Cu' compounds discussed in this work are the first examples of such complexes incorporating either the MeGapz₃⁻, HBpz₃⁻ or C₅H₅⁻ ligands in which the 3:3:1 arrangement has been demonstrated unequivocally. The novel tridentate unsymmetric ligands Me₂GapzO(C₅H₃N)CH₂NMe₂⁻ (L[sub a]⁻) and Me₂GapzO(C₉H₆N)⁻ (L[sub q]⁻) have been prepared and numerous transition metal compounds containing these ligands synthesized. The compounds L[sub a] M(CO)₃(M = Mn or Re) are the first examples of transition metal carbonyl complexes in which both the fac and mer arrangements of the unsymmetric ligand about the central metal have been found to co-exist in solution. The square planar rhodium(I) complex, L[sub q]Rh(CO) has been shown to add Mel oxidatively, followed by facile methyl migration reaction to produce the five-coordinate Rh(III) acetyl derivative, L[sub q]Rh(COMe)I. In contrast, the reaction of L[sub a]Rh(CO) with Mel, led to the six-coordinate Rh(III) oxidative addition product, L[sub a]Rh(Me)(I)CO.
Science, Faculty of
Chemistry, Department of
Graduate

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36

Ndamyabera, Christophe Adrien. „Porous metal complexes for CO2 capturing“. University of the Western Cape, 2017. http://hdl.handle.net/11394/5739.

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Magister Scientiae - MSc (Chemistry)
The need in energy has resulted in the burning of fossil fuels at an increasingly high level. The consequence is a release of high volumes of carbon dioxide gas (CO2) in the atmosphere. This gas is a major greenhouse gas which causes global warming. There is therefore a great need to efficiently sequestrate this gas (CO2) for a sustainable economic development and environment. A new class of metal organic frameworks (MOFs) is a promising high potential application in carbon dioxide capture. In the current study, synthetic methods were developed for the design of porous cobalt succinates and nickel hydroxy-terephthalates for CO2 adsorption. The methods developed and interrogated include, sonication, hydrothermal synthesis (at room temperature, reflux and Parr reactor), and microwave synthesis. The conventional cobalt chloride hexahydrate was substituted by cobalt acetate for synthesis at room temperature. Cobalt acetate was used to replace cobalt chloride in the synthesis of cobalt succinate at room temperature and led to a new cobalt succinate complex (CoS-Ac). The complexe CoS-Ac differs from CoS synthesized from cobalt chloride hexahydrate. Synthesis of cobalt succinate via sonication (CoS-sn) was achieved in 45 min and the structure of the complex was different when synthesized via the hydrothermal route (under reflux) abbreviated CoS-th.

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37

Cheung, Wai Man. „Transition metal complexes with dichalcogenoimidodiphosphinate ligands /“. View abstract or full-text, 2007. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202007%20CHEUNG.

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38

Smith, Amanda Michelle. „Metal complexes of xylylene-bridged pyridiones“. Thesis, Imperial College London, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.362871.

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39

Dubberley, Stuart R. „New calix[4]arene metal complexes“. Thesis, University of Oxford, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365290.

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40

Redfern, C. M. „Electronic structure of transition metal complexes“. Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.235094.

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41

Casely, Ian J. „Electropositive metal N-heterocyclic carbene complexes“. Thesis, University of Edinburgh, 2009. http://hdl.handle.net/1842/3873.

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The first chapter is an introduction to the f-elements, with a focus on the synthesis and chemistry of tetravalent cerium complexes. The synthesis, characterisation and reactivity of carbenes, particularly N-heterocyclic carbenes (NHCs), and anionic-functionalised NHC ligands is discussed. The synthesis and reactivity of s-block, Group three and fblock NHC complexes is reviewed. The synthesis of the alcohol-functionalised unsaturated imidazolium proligand, [H2L]I [H2L = HOCMe2CH2(1-CH{NCHCHNiPr})], is extended to saturated imidazolinium analogues, [H2LR]X, [HOCMe2CH2(1-CH{NCH2CH2NR})]X (R = iPr, abbreviated to P; R = Mes, abbreviated to M; R = Dipp, abbreviated to D, X = Cl, I). Mono-deprotonation results in the isolation of bicyclic imidazolidines HLR, which can be ring-opened and silylated by treatment with Me3SiI, to afford [HLR, OSiMe3]I, R = iPr and Mes. Further deprotonation of HLR with MN"2 (M = Mg, Zn; N" = N(SiMe3)2) affords LRMN" (M = Mg and Zn) and ZnLR 2. These complexes proved active for the polymerisation of raclactide at room temperature without the need for an initiator. The third chapter focuses on cerium chemistry. Repetition of the literature synthesis of CeIV tert-butoxide compounds affords the unsolvated Ce(OtBu)4 and also the cluster Ce3(OtBu)11. Treatment of Ce(OtBu)4 with HL did not yield a CeIV-NHC complex, but one bearing a tethered imidazolium group, (OtBu)3Ce( -OtBu)2( -HL)Ce(OtBu)3. The synthesis of a CeIII-NHC complex, CeL3, and the oxidation of this forms an unprecedented CeIV-NHC complex, CeL4, via ligand redistribution; the complex contains two bidentate ligands and two alkoxide-tethered free NHC groups. Functionalisation of the free NHCs with boranes affords the adducts Ce(L)2(L-B)2, where B = BH3 or 9-BBN (9-Borabicyclo[3.3.1]nonane). A number of cerium complexes of the saturated-backbone NHC, LR, LRCeN"2 and LR 2CeN", have been synthesised and their oxidation chemistry and reactivity investigated. The final chapter contains an NMR study of the synthesis of a series of yttrium LR adducts, LP xYN"(3-x) (x = 1, 2 or 3), and of the synthesis of uranium complexes LRUN"2, R = Mes or Dipp, including a range of small molecule reaction chemistry. The uranyl NHC complexes, UO2LR 2, R = Mes or Dipp, have also been synthesised and characterised; these possess very high frequency carbene carbon chemical shifts.

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42

Hollingsworth, Nathan. „Metal complexes of amino-functionalised alkoxides“. Thesis, University of Bath, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.528128.

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43

O'Sullivan, Julie Ann. „Metal complexes of trimethylsilyl substituted cyclooctatetraenes“. Thesis, University of Sussex, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.361361.

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44

Davoile, Ryan J. „New reactions of metal-alkyne complexes“. Thesis, Loughborough University, 2003. https://dspace.lboro.ac.uk/2134/12908.

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This thesis describes the use of bimetallic alkyne complexes for use in variants of the Nicholas reaction. The heterobimetallic core provides a source of chiral control unlike previous protocols reported in the literature, as stereocontrol arises from the inherently chiral cobalt-molybdenum core of these complexes and not from an external source. The inherently chiral heterobimetallic complexes were utilised as efficient chiral auxiliaries for nucleophilic additions to both propargylic alkene and Nicholas salt complexes with a degree of stereocontrol also extending to intramolecular addition. 1,3-Dipolar cycioaddition to homo bimetallic and heterobimetallic enyne complexes to obtain isoxazoline ring systems was investigated, following a report in the literature. A novel homobimetallic 1,3-dipole was synthesised on opening of a cyclopropane, subsequel1tly trapping with a series of aldehyde and imines to efficiently form tetrahydrofuran and pyrrolidine ring structures. Chapter 1: An overview of developments of homobimetallic alkyne complexes in the Nicholas reaction as reported in the literature. Chapter 2: Highlights our research into the use of bimetallic alkyne complexes for use in organic synthesis. Chapter 3: Provides experimental data for our studies.

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45

Mobbs, B. E. „Arene transition metal complexes in synthesis“. Thesis, University of Oxford, 1985. http://ora.ox.ac.uk/objects/uuid:4c7030d4-297e-4af8-a622-d5b4963fc0a3.

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This thesis deals with the applications of organopalladium and organochromium chemistry to the functionalisation of the benzopyran ring system, at a variety of oxidation levels. Section I demonstrates the functionalisation of 3-, 6-, and 8-bromochromones via palladium (0) insertion into the C-Br bond. The resultant arylpalladium species are shown to undergo addition to the least substituted end of a variety of olefins including methyl acrylate, acrylonitrile and styrene. Subsequent palladium-hydride elimination leads to overall palladium catalysed vinylation of the chromone and the synthesis of a number of novel compounds. Vinylation occurs regiospecifically at the site of chromone bromination and is shown to allow clean substituent introduction into each of the three sites. The palladium catalysed reaction of 3,6-dibromo-chromone with methyl acrylate leads to vinylation at both the C3 and C6 positions. Carbonylation of the 6-bromochromone in ethanol or butanol leads to the 6-ethyl or 6-butyl esters respectively. The palladium catalysed vinylation of the 6-bromochromone with ethyl vinyl ether leads to a mixture of products from addition of the chromone to either end of the olefin. With p-bromophenol or p-bromo-N,N-dimethylaniline the reaction gives exclusively the acetylated product arising from addition to the more substituted end of the olefin. This change in orientation is rationalised by considering the polarisation of the olefin and the arylpalladium species. Section II demonstrates the functionalisation of chroman and 4-chromanol via coordination to the Cr(CO)₃ moiety. (η⁶-Chroman)Cr(CO)₃ is synthesised and is shown to undergo regiospecific ring deprotonation at C8 under kinetic conditions or regiospecific benzylic deprotonation at C4 under thermodynamic conditions. The resultant anions are quenched with alkyl halides, aldehydes, Eschenmoser's salt and methyl disulphide resulting in selective functionalisation of either site. No mixed products are observed. The uncomplexed arene is shown to be totally unreactive under identical conditions. (η⁶-4-Chromanol)Cr(CO)₃ is synthesised and is shown to undergo regiospecific C8 ring deprotonation by comparison with authentic samples of the C5 and C8 methylated alcohols. Protection of the hydroxyl group as its methyl, t-butyldimethylsilyl or methoxymethyl ethers is found not to alter the regiochemistry of deprotonation. The 4-chromanol t-butyldimethylsilyl and tri-i-propylsilyl ethers are synthesised and coordinated to the metal unit. Cleavage of the silyl ethers is shown to proceed with loss of stereochemistry, indicating C-0 bond cleavage.

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46

Foster, Clive Edwin. „Tailored metal complexes for imaging applications“. Thesis, Durham University, 1996. http://etheses.dur.ac.uk/5223/.

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The short-lived PET radionuclide (^134)La(t(_1/2)=6.7 minutes) is well suited to the repeated evaluation of blood perfusion, thus providing a method of following changes in tumour behaviour, in response to therapy. Ligands, both acyclic and macrocyclic, have been synthesised, and the complexes formed with (^134)La(^3+) evaluated in vitro and in vivo. Other lanthanide complexes have also been evaluated for potential use in magnetic resonance imaging and photoimmunoassay studies. A preliminary crystal structure determination of a lanthanum tetrabenzylphosphinate complex reveals the presence of one water molecule in the inner co-ordination sphere. The development of monoclonal antibodies with a specificity for the surface features of tumour cells presents a method for the localisation of a radionuclide at the tumour. Copper-64 (t(_1/2)=12.7 hours) uniquely combines the decay properties required for imaging and therapy. Ligands have been developed for derivatising antibody molecules with radioactive copper, whilst retaining specificity for the target antigen. Three modified proteins have been evaluated in vivo, and show a high tumour uptake compared with blood, but modest uptake compared with the liver, suggestive of some degree of protein denaturation during labelling. A more subtle approach has been developed, exploiting the affinity of biotin for avidin. Higher selectivity at much shorter post-administration time is potentially attainable by the use of a multi-step procedure. A copper binding ligand incorporating biotin has been synthesised. The (^64)Cu complex of the conjugate shows specificity for the protein avidin both in vitro and in vivo. The prognosis of patients with hepatoma or liver metastases is poor. A lipophilic copper complex has been synthesised and retention in the liver demonstrated in vivo. Measurements with three cell lines in vitro suggest that the complex is more readily taken up by tumour cells (and cells from metastases) compared to normal cells.

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47

Bridgewater, Brian Michael. „Sterically hindered chiral transition metal complexes“. Thesis, Durham University, 1998. http://etheses.dur.ac.uk/5022/.

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This thesis describes the synthesis, characterization and study of a series of organometallic compounds which all contain the same new ligand, l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyl. The ligand forms a chiral complex once coordinated, and is relatively bulky when compared with ligands such as cyclopentadienyl or 4,5,6,7-tetrahydroindenyl.Chapter one of this thesis introduces cyclopentadienyl ligand chirality, cyclopentadienyl metal complex chirality and sterically demanding cyclopentadienyl systems. The synthesis and chemistry of tetrahydroindenes and some applications of chiral cyclopentadienyl metal complexes and their bulky analogues are also reviewed. Chapter two describes modifications to a literature preparation of the tetrahydroindenone precursor of the new tetrahydroindenyl ligand which lead to higher yields. The synthesis of the ligand itself is described, as well as the synthesis of a benzylidene-substituted hexahydroindene, which demonstrates a limitation in the flexibility of the synthetic route chosen. The synthesis, characterization and various properties of the following iron(II) compounds are discussed in chapter two; bis-l-phenyl-3-methyl- 4,5,6,7-tetrahydroindenyl iron (II), 2.3, l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyl iron(II) dicarbonyl dimer, 2.4, and l-phenyl-3-methyl-4,5,6,7-tetrahydroindaiyl methyl dicarbonyl iron(II), 2.5. For all these iron complexes, the solid state molecular structures and the absolute configuration of the chiral ligand were determined using single crystal X-ray d iffraction. For 23 and 2.4, three isomers are possible, two enantiomers that are collectively termed the rac-isomer and a third isomer, the meso- isomer. Cyclic voltammetric studies on 2.3 indicate that it has a reversible one electron oxidation at 0.187 V (with respect to a non-aqueous Ag/AgCl standard electrode). The difference between this and the reversible one electron oxidation for (η-C(_5)H(_5))(_2)Fe (with respect to the same standard) is -0.314 V, therefore 2.3 is shown to be much more easily oxidized than (η-C(_5)H(_5))(_2)Fe. The solution-state infi-a-red spectrum of 2.4 is explained, with reference to a literature analysis of the unsubstituted analogue [CpFe(CO)(_2)](_2). The steric forces present in the various molecular environments are discussed in connection with the degree of phenyl-ring tilt relative to the cyclopentadienyl mean plane and the deviation of the other cyclopentadimyl substituents away from the metal centre. Subsequent reactions of compounds 2.4 and 2.5 are described. Attempts to make linked analogues of the new ligand are summarized in chapter two. In chapter three, two Zr(rV) compounds are prepared, bis (l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyi) zirconium(fV) dichloride, 3.1, and bis (l-phenyl-3-methyl-4,5,6,7-tetrahydroindenyl) dimethyl zirconium(TV), 3.2. Upon crystallization, rac-3.1 spontaneously resolves into crystals containing only one enantiomer. The similarities and differences in the spectroscopic data for the iron(n) compounds of chapter two and the zirconium(IV) compounds of chapter three are discussed and possible explanations offered . The solid state molecular structures of 3.1 and 3.2 were determined by single crystal X-ray diffraction. Experimental details are given in chapter four, whilst the characterizing data are presented in chapter five. Details of the X-ray structure determinations are given in Appendix A.

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48

Williams, James Anthony Gareth. „Luminescence behaviour of macrocycle metal complexes“. Thesis, Durham University, 1995. http://etheses.dur.ac.uk/5313/.

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Luminescent complexes of lanthanide ions are of growing interest because the long lifetime of emission allows time-resolved detection procedures to be employed. A key step in the development of such systems lies in the preparation of highly luminescent complexes which display high stability in aqueous solution. A series of ligands based on 1,4,7,10-tetraazacyclododecane have been prepared, in which the nitrogen atoms are appended with coordinating phosphinate or amide groups, or a combination of both. The compounds obtained are octadentate ligands which form water-soluble lanthanide complexes of high stability. Complexes incorporating aryl groups in the pendent arms have been prepared and some display intense metal luminescence following excitation into the organic chromophores. A back energy transfer process occurs in the terbium complexes containing naphthyl or quinohnone groups. Measurements of the luminescence lifetimes in H(_2)O and H(_2)O show diat diere are no metal-bound water molecules in the tetrabenzylphosphinate complexes. Those incorporating one amide and three phosphinate groups display hydration states between 0 and 1. An attempt has been made to correlate this information with that obtained from an analysis of the nuclear magnetic resonance dispersion profiles of related gadolinium complexes. The complexes incorporating secondary amide groups display an additional deactivation pathway for the metal excited state involving energy transfer into N-H bonds. The luminescence behaviour of four macrocyclic tetraamide ligands incorporating naphthyl fluorophores has been studied. These compounds exhibit distinctive changes in luminescence in the presence of quenching (eg. Pb(^2+), Cu(^2+) and Ni(^2+)) and non- quenching ions (eg. Cd(^2+) and Zn(^2+)). This behaviour extends to non-aqueous solution. The protonated tetranaphthyl ligand forms an intramolecular excimer in which the excimer emission displays a sensitive dependence on the polarity of die solvent.

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49

Norbert, Waranakulaarachchiralalage D. J. A. „Metal complexes as potential pH sensors“. Thesis, Queen's University Belfast, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.336008.

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50

Baiada, A. „Novel tricoordinate univalent coinage metal complexes“. Thesis, University of East London, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375666.

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