Tesis sobre el tema "Polydentate ligands"
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1
Graham, Todd Warren. "Mixed-metal complexes incorporating polydentate bridging ligands". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0028/NQ39533.pdf.
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Khan, Fatima K. "Coordination of polydentate ligands in organometallic clusters". Thesis, University of Cambridge, 1992. https://www.repository.cam.ac.uk/handle/1810/272800.
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Chen, Yang. "The syntheses and reactivity of polydentate PNNP ligands and macrocyclic polyphosphine ligands". HKBU Institutional Repository, 1998. http://repository.hkbu.edu.hk/etd_ra/220.
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Elder, Susan Margaret. "The coordination chemistry of some polydentate nitrogen-donor ligands". Thesis, University of Cambridge, 1990. https://www.repository.cam.ac.uk/handle/1810/272957.
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Ireland, David Rey. "Copper(II) and Ruthenium(II) Complexes from Polydentate Ligands". University of Dayton / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1523008522727672.
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Smith, Charles J. "Transition metal complexes on novel, polydentate, water-soluble, phosphine ligands /". free to MU campus, to others for purchase, 1997. http://wwwlib.umi.com/cr/mo/fullcit?p9841335.
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Movahed, Hazel Haghighi. "Coordination chemistry and crystal engineering with new polydentate pyrazole-based ligands". Thesis, University of Sheffield, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.522425.
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Das, Ananya. "Novel transition metal complexes of some B-cyclodextrin based polydentate ligands: synthesis and physico-chemical characterization". Thesis, University of North Bengal, 2021. http://ir.nbu.ac.in/handle/123456789/4333.
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黎寶韻 y Po-wan Lai. "Synthesis, structural characterization and photophysical properties oflanthanide complexes containing polydentate amide ligands". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2001. http://hub.hku.hk/bib/B42576180.
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Whitehead, Martina. "Synthesis of polydentate ligands and the formation of heterometallic and circular helicates". Thesis, University of Huddersfield, 2010. http://eprints.hud.ac.uk/id/eprint/9643/.
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Described herein, is the synthesis and coordination chemistry of seven novel ligands L1 - L7. These ligands form metallosupramolecular assemblies upon coordination of transition metal ions resulting in heterodi- and hetreotrimetallic double helicates and penta- and tetranuclear cyclic helicates. Described in Chapter 2 is a new class of ditopic segmental pyridyl-thiazole(py-tz) N-donor ligands L1 - L3. Reaction of L1 with ZnII ions results in the formation of a dinuclear double helicate [Zn2(L1)2]4+. Reaction of L2 with either ZnII or HgII results in the formation of the L2-containing dinuclear double helicates [Zn2(L2)2]4+ and [Hg2(L2)2]4+. However, reaction with both ZnII or HgII results in the sole formation of the heterodimetallic helicate [HgZn(L2)2]+. Both metal ions are 6-coordinate but the HgII ion is coordinated by the two py-tz-py units whereas the ZnII ion is coordinated by the py-py-tz domain. The reason that these isomeric sites have different preferences for each of the metal ions is due to the position of the thiazole unit within the terdentate domains, as in the central position the thiazole unit increases the “bite angle” of the donor unit making it more suitable for the larger HgII. Conversely the py-py-tz domain has a smaller bite angle and it more suited to the smaller ZnII ion. Reaction of L3 with ZnII, HgII and CuII results in the formation of a heterometallic trinuclear double helicate [HH-[HgCuZn(L3)2]5+. In a similar fashion to L2, the ZnII ion coordinated by the terdentate py-py-tz domain and the HgII coordinated by the py-tz-py domain. The central bipyridine unit coordinates the tetrahedral CuII ion resulting in the first reported example of a heterotrimetallic double helicate. Described in Chapter 4 is a potentially hexadentate N-donor ligand L4, which upon reaction with CdII results in the formation of a dinuclear double helicate [Cd2(L4)2]4+. In this structure the ligand partitions into two tridentate tz-py-py domains each of which coordinate a different metal ion. However, reaction of L4 with ZnII results in the formation of a pentanuclear circular helicate [Zn5(L4)5]10+, with all the five zinc ions adopting a octahedral coordination geometry arising from the coordination of the two tridentate tz-py-py domains from two different ligand strands. This difference in structure is attributed to unfavourable steric interactions which prevent the formation of [Zn2(L4)2]4+ but these unfavourable interactions are not present with the larger Cd2+ ion. Described in Chapter 5 are the potentially pentadentate and tetradentate ligands L5 and L6, respectively. The ligand L5 contains both a bidentate and tridentate binding site separated by a phenylene spacer unit. Reaction of L5 with CuII results in the formation of a pentanuclear circular helicate [Cu5(L5)5]10+. Each of the CuII ions adopts a 5-coordinate geometry formed by coordination of the bidentate domain of one ligand strand and the tridentate domain of a different ligand. As a result this gives a head-to-tail pentanuclear double helicate. Reaction of L6 and L4 (Chapter 4) with CuII results in the formation of a heteroleptic pentanuclear circular helicate [Cu5(L4)3(L6)2]10+. The cyclic array consists of five copper(II) ions, coordinated by three strands of L4 and two strands of L6. In this species four of the CuII adopt a 5- coordinate geometry arising from coordination of a tridentate domain from L4 and a bidentate domain from L6. The remaining copper ion is coordinated by two tridentate domains from L4 resulting in an octahedral coordination geometry. Described in Chapter 6 is the potentially hexadentate N-donor ligand L7 which comprises of two identical tridentate py-py-tz N3 binding domains separated by a pyrene unit. Reaction of L7 with ZnII results in the formation of a tetranuclear circular helicate [Zn4(L7)4]8+ with all four zinc metal ions adopting a six-coordinate geometry arising from the coordination of two tridentate pypy- tz units from two different ligand strands. The formation of this lower nuclearity species (e.g. tetranuclear rather than pentanuclear) is attributed to the p-stacking between the pyrene unit and the py-py-tz domain.
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Holmes, J. M. "Coordination chemistry of polydentate chelating ligands incorporating the alpha,alpha'-diimine moiety". Thesis, University of Cambridge, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.355867.
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Gaab, Manuela. "Second generation Trisoxazolines : new polydentate and recyclable dendritic ligands for asymmetric catalysis". Strasbourg, 2009. https://publication-theses.unistra.fr/public/theses_doctorat/2009/GAAB_Manuela_2009.pdf.
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Le présent travail, axé sur un élargissement et une optimisation des applications des ligands de type tris(oxazolinyl)ethane (trisoxazolines) en catalyse asymétrique « acide de Lewis », présente une panoplie de nouveaux ligands stéréodirecteurs multidentates et porteurs de fonctions capables de permettre d’ultérieurs connexions ou autre greffage (« linkers »). Basé sur la préparation (à l’échelle du gramme) de précurseurs fonctionnalisés de la classe des alcools aminés appropriés, trois dérivés chiraux pentadentates de symétrie C1 et deux dérivés hexadentates de symétrie C3 de la famille des trisoxazolines, incorporant des fonctions (thio)ether, ont pu être synthétisés. Conférant de meilleures stabilités cinétiques envers les métaux labiles comme les lanthanides, ces nouveaux ligands sont alors supposés fournir des applications plus efficaces dans les transformations stéréosélectives. Les bis- et trisoxazolines contenant une fonction alkynyl ont pu être greffées de façon covalente à des supports dendritiques de type carbosilane et le potentiel catalytique des complexes de cuivre(II) de ces nouveaux ligands polydispersés a pu être examiné au travers de l’étude de deux réactions de référence. Pour chacune de ces réactions, les catalyseurs multisites de type bisoxazoline montrent une meilleure sélectivité et plus particulièrement, une activité catalytique supérieure. Cette observation peut être interprétée comme étant due à une gêne dans la décoordination de la troisième unité oxazoline, représentant l’étape clé pour la génération de l’espèce catalytiquement active pour les complexes de cuivre porteurs de ligands trisoxazoline immobilisés. Les catalyseurs dendritiques de seconde génération ont été encapsulés dans des sachets à membranes de dialyse. Ainsi, les réactions catalytiques ont pu être effectuées en immergent ces « sachets catalytiques » dans un récipient contenant une solution de substrat. Les catalyseurs contenant les unités bisoxazoline ont ainsi conduits à de bons résultats reproductibles après plusieurs recyclages, alors que la performance des dendrimères contenant les ligands trisoxazoline diminue de manière monotone au fil des tours catalytiques en raison de leur faible activité, nécessitant alors une augmentation du temps de réaction après chaque cycle. Par conséquence, ceci engendre une perte plus importante du catalyseurIn this work, directed towards more efficient and broadened applications of tris(oxazolinyl)ethanes (trisoxazolines) in asymmetric Lewis acid catalysis, a library of new stereodirecting polydentate and linker-functionalised ligands was designed. On the basis of a multigramm-scale access to appropriately functionalised α-amino alcoholprecursors, three C1-chiral pentadentate and two C3-symmetric hexadentate trisoxazoline derivatives, incorporating peripheral (thio)ether functions, were synthesised. Conferring greater kinetic persistence to labile metals such as lanthanides, they are assumed to allow efficient applications in stereoselective transformations. Bis- and trisoxazolines containing an alkynyl unit have been covalently attached to carbosilane dendrimers and the general catalytic potential of their CuII-complexes was assessed by studying two benchmark reactions. For both of them, the bisoxazoline-based multisite catalysts displayed superior selectivity and, in particular, catalyst activity. The latter was interpreted as being due to the hindered decoordination of the third oxazoline unit, the key step in the generation of the active catalyst, in the immobilised trisoxazolinecopper complexes. Second generation dendrimer catalysts were immobilised in dialysis membrane bags, allowing to effect catalytic conversions by dipping them into substrate-filled reaction vessels. The bisoxazoline-based catalysts gave good and reproducible results after several recyclings, whereas the performance of the trisoxazoline dendrimers decreased monotonically due to their low activity, which necessitated an increased reaction time for each cycle. This resulted in higher levels of catalyst leaching
Im Rahmen dieser Arbeit wurde, mit dem Ziel Tris(oxazolinyl)ethanderivate (Trisoxazoline) in der asymmetrischen Lewissäure-Katalyse effizienter und breiter anzuwenden, eine Serie neuer polydentater und Linker-funktionalisierter Steuerliganden synthetisiert. Basierend auf einem Zugang zu entsprechend funktionalisierten α-Aminoalkoholvorstufen im Multigramm-Maßstab wurden drei C1-chirale pentadentate und zwei C3-symmetrische hexadentate Trisoxazolinderivate mit peripheren (Thio)etherfunktionen synthetisiert. Diese tragen im Prinzip zur kinetischen Stabilisierung labiler Metalle, z. B. Der Lanthanoiden, bei und ermöglichen so deren effiziente Anwendung in stereoselektiven Reaktionen. Nach der kovalenten Trägerung Alkinyl-funktionalisierter Bis- und Trisoxazoline an Carbosilandenrimeren wurde das katalytische Potential ihrer CuII-Komplexe in zwei Benchmarkreaktionen abgeschätzt. Bisoxazolin-basierte Vielzentrenkatalysatoren erzielten mit beiden Systemen höhere Selektivitäten und insbesondere Aktivitäten als ihre Trisoxazolinanaloga. Dies wurde auf die gehinderte Dekoordination des dritten Oxazolins, dem Schlüsselschritt bei der Ausbildung des aktiven Katalysators im Falle der immobilisierten Trisoxazolin-Kupferkomplexe, zurückgeführt. Dendritische Katalysatoren der zweiten Generation wurden in einer Dialysemembran immobilisiert, um durch Eintauchen der resultierenden Beutel in mit Substrat befüllte Reaktionsgefäße katalytische Umsetzungen durchzuführen. Dabei erzielten die Bisoxazolinbasierten Katalysatoren über mehrere Läufe gute, reproduzierbare Werte, während jene der Trisoxazolindendrimere monoton abnahmen. Dies ließ sich auf ihre geringe Aktivität, die damit verbundenen längeren Reaktionszeiten und die erhöhten Katalysatorverluste durch Leaching zurückführen
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Lai, Po-wan. "Synthesis, structural characterization and photophysical properties of lanthanide complexes containing polydentate amide ligands". Click to view the E-thesis via HKUTO, 2001. http://sunzi.lib.hku.hk/hkuto/record/B42576180.
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Hollis, Emmalina. "The development and application of new polydentate ligands in early thransition metal chemistry". Thesis, University of Oxford, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.496915.
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Gamboa, Martinez Sergio Aaron. "Lewis acidic metal complexes with polydentate ligands for the preparation of biorenewable polymers". Thesis, University of Edinburgh, 2014. http://hdl.handle.net/1842/8993.
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Due to the ever increasing necessity to reduce our dependence on fossil fuels as feedstocks for polymeric materials, the work presented herein describes the investigation of new metal complexes as initiators for the formation of polyesters and polycarbonates from renewable monomers. These polymers are regarded as biodegradable and have the properties required to replace traditional plastics in applications such as food packaging, electronic devices, and medical biomaterials. Chapter one introduces previous literature relevant to the research on which this study focuses; ligands based on alkoxides, phosphine oxides and N-heterocyclic carbenes with alkoxide or amino pendant groups, as well as the metal complexes in which they are used. Current methods of polymerisation and copolymerisation and the initiators utilised are also examined. Chapter two contains the design and synthesis of [M(LR n)]m metal complexes where LR is [(R)2P(O)CH2CH(tBu)O]– and R is Ph or tBu. Divalent metal centres such as CoII and ZnII have been used for the formation of the studied compounds. Studies on their reactivity as initiators for polymerisations are also described. Chapter three presents the utilisation of di- and tridentate ligands, with one or two NHC species respectively, for the synthesis of [Mx(LY n)], where M is CuI, ZnII or TiIII and LY is an alkoxy-tethered NHC species or a ‘CNC’ tridentate ligands with an amino derivative as bridge. Their reactivity and ability to act as initiators for polymerisation reactions was also examined. Chapter four comprises overall conclusions of this work and the impact of these investigations. Chapter five outlines the experimental details and data for the compounds presented.
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Tse, Man Chung. "Preparation and reactivity of transition-metal complexes of polydentate ligands containing both amino and phosphino functional groups". HKBU Institutional Repository, 1995. http://repository.hkbu.edu.hk/etd_ra/46.
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Bullock, Samantha Jane. "Metallosupramolecular chemistry of polydentate ligands and the solid state studies of diphenylcarbazide and dithizone". Thesis, University of Huddersfield, 2014. http://eprints.hud.ac.uk/id/eprint/24695/.
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Described herein, is the synthesis and coordination chemistry of eight novel ligands L1-L8, and the solid state studies of diphenylcarbazide and dithizone. These ligands form metallosupramolecular assemblies upon coordination of transition metal ions resulting in a wide range of architectures. Described in chapter two is a series of ligands that contain both N-donor and N-oxide donor atoms, L1-L4. Reaction of L1 with Cu2+ results in the formation of a mononuclear complex [Cu(L1)(ClO4)2(sol)] (solvent = MeCN or H2O), whereas L2 forms the dinuclear double helicate [Ni2(L2)2]4+ with Ni2+. Reaction of L3 with Cu2+ results in the formation of a head-to-tail dinuclear double helicate [Cu2(L3)2]4+. The N-oxide units imparts flexibility in the ligand strand and where the unoxidised ligand strand forms a circular helicate, the incorporation of an N-oxide unit allows the formation of the dinuclear double helicate. Reaction of L4 with Co2+ results in the formation of a tetranuclear circular helicate [Co4(L4)4]8+. Analogous complexes that contain ligands with a 1,3-phenyl spacer unit give pentanuclear circular helicates, whereas with a 1,3-phenol spacer the lower tetranuclear species is observed. The difference in the nuclearity of the circular helicates is due to the steric bulk of the methyl group on the central phenol spacer. In the dinuclear double complex formed with L3 the N-oxide unit allows the ligand to flex, whereas the steric bulk of the –OH unit in L4 is sufficiently large that even with the added flexibility that the N-oxide units imparts a double helicate cannot be formed. Chapter three introduces a new class of polydentate ligands, L5-L7, these ligands consist of N-donor domains separated by a 1,3-phenol unit. The ligand L5 contains two identical tridentate N-donor domains, reaction of L5 with Zn2+ results in a tetranuclear circular helicate [Zn4(L5)4]8+. Within the structure all four Zn2+ ions are six-coordinate, arising from the coordination of two tridentate domains from two different ligand strands. Reaction of L6 with Ag+ results in the formation of the dinuclear double meso-helicate [Ag2(L6)2]2+. Reaction of L6 with Cd2+ produces a crystalline material that consists of both colourless and orange species. The colourless crystals correspond to the mononuclear complex [Cd(L6)2(MeCN)2]2+, whereas the orange crystals produce the dinuclear double meso-helicate [Cd2(L6)2]2+. This variation in self-assembly is a direct result of the –OH unit on the 1,3-phenol spacer; if the -OH unit is protonated the oxygen atom can only coordinate once and therefore the mononuclear complex forms, however deprotonation of one of the -OH unit results in the oxygen coordinating twice as a bridging donor to form the dinuclear complex. Both the [Cd(L6)2(MeCN)2]2+ and [Cd2(L6)2]2+ species are present in solution, under equilibrium conditions, varying the stoichiometry alters the predominant species. The ligand L7 is unsymmetrical, upon reaction with Co2+ the ligand partitions into two different binding sites; a tridentate N-donor domain and a tridentate domain consisting of the bidentate N-donor domain and the O-donor atom from the central 1,3-phenol spacer. The resulting dinuclear HH-[Co2(L7)2]3+ complex demonstrates that the two cobalt metal centres occupy different binding sites. Examining the solid state X-ray crystallographic data suggests that the two cobalt metal centres in the [Co2(L7)2]3+ complex occupy different oxidation states; Co2+ and Co3+ to give a mixed valence helicate. In an analogues fashion to L6, reaction of L7 with Zn2+ produces a crystalline material that consists of both colourless and orange species. The colourless crystals correspond to the mononuclear complex [Zn(L7)2]2+, whereas the orange crystals produce the dinuclear double helicate [Zn2(L6)2]3+. In the mononuclear [Zn(L7)2]2+ species the Zn2+ metal centre is coordinated by the tridentate N-donor domain of two different ligands. In the dinuclear [Zn2(L6)2]3+ species each Zn2+ metal centres is coordinated by the tridentate N-donor domain of one ligand and the tridentate domain, consisting of the bidentate N-donor and the O-donor from the central 1,3-phenol spacer, from another different ligand. The variation in the self-assembly is a direct result of the stoichiometry of the reaction; the formation of these two complexes is under the same equilibrium conditions of the previous L6 structures. Described in chapter four is the potentially pentadentate N-donor ligand L8, which comprises of a bidentate and tridentate binding domains separated by a 1,3-pyrene spacer. Reaction of L8 with Cu2+ results in the formation of a tetranuclear circular helicate [Cu4(L8)4]8+. Each of the Cu2+ ions adopts a 5-coordinate geometry formed by the coordination of the bidentate domain of one ligand strand and the tridentate domain of a different ligand strand, resulting in a head-to-tail tetranuclear circular helicate. The formation of this head-to-tail circular helicate is a result of the 1,3-pyrene spacer preventing the formation of the linear double stranded assemblies and secondly the stereoelectronic preference of Cu2+. Chapter five reports the solid state studies of diphenylcarbazide and dithizone, which are both useful reagents for the colorimetric determination of a variety of different metal ions. Examination of the scientific literature over the past 100 years shows that the coordination chemistry of DPC and DPTC is inconsistent, with literature sources proposing contradictory and non-definitive explanations, this chapter aims to extend the knowledge surrounding these reagents by isolating crystals. DPC reacts with Cd2+ to form the mononuclear species [Cd(DPC)2]2+ the two ligands are coordinating through both the N-donor and O-donor domains. The discrepancies surrounding the DPC reaction is whether the redox reactions between the metal and ligand occur, upon reaction of DPC and Cd2+ the metal does not oxidise the ligand. Reaction of DPC and Cu2+ is more complex than the previous Cd2+ reaction, the resulting [Cu3OH(OH2)3(DPTO)6]5+ structure comprises of six ligands and three metal ions. DPC undergoes oxidative intramolecular cyclisation to form the nitrogen containing heterocycle 2,3-diphenyltetrazolium-5-olate (DPTO) and coordinates the Cu2+ metal centre in two different modes: via both the oxygen and amide nitrogen atoms or by the bridging carbonyl unit. The [Cu3OH(OH2)3(DPTO)6]5+ structure is also generated when reacting DPCO with Cu2+. Unfortunately a crystal of a chromium or vanadium complex with DPC was not achieved; however the cyclised ligand was isolated, highlighting that the oxidation and cyclisation of DPC is important in the coordination chemistry of these ions. Reaction of the sulphur derivative DPTC with various metal ions results in the deprotonation of the ligand to form the monoanionic species, which coordinates the metal ions via the S-donor and azo N-donor atoms. Reaction of DPTC with Hg2+ to form the mononuclear complex [Hg(DPTC)2]. The simple mononuclear complex involves two DPTC ligands coordinating the four-coordinate Hg2+ ion as a bidentate donor via the N-donor and S-donor atoms. The reaction of DPTC with both Hg2+ and Ag+ results in an interesting structure containing two Ag+, two Hg2+ and four DPTC ligands. The DPTC appears to first react with Hg2+ to form the previous [Hg(DPTC)2] complex, this then acts as a bidentate ligand, coordinating via the S-donor atom and the Hg2+ itself to form the [Hg2Ag2(DPTC)4(acetone)2(ClO4)2] complex. The reaction of DPTC with Cu2+, whether the anion is perchlorate or tetrafluoroborate, results in a very interesting structure, which comprises of eight DPTC ligands and eight Cu+ metal ions. The reaction of Cu2+ with DPTC results in the metal ion reducing to Cu+ and simultaneously the DPTC deprotonates to form the monoanionic form. The counter-anion acts as a template and the formation of the “Cu8” is a result of the presence of the anion. Reaction of copper (II) acetate with DPTC results in the [Cu2(DPTC)2(DPTCO)] complex. The structure contains three ligands and two reduced distorted tetrahedral Cu+ ions. Each Cu+ ion has four-coordinate geometry arising from the coordination of two different forms of the DPTC ligands. Two of the ligands present are the monoanionic DPTC, coordinating via the S-donor and terminal N-donor azo atoms. Whereas the third ligand has completely oxidised to form DPTCO, coordinating via both the terminal N-donor azo N-donor atoms, the sulphur atom bridges both of the metal ions.
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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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Zhang, Lilu. "Synthesis and chemistry of lanthanide complexes with phosphorus ylides, amides or porphyrinate ligands, and of transition metal complexes with polydentate ligands". HKBU Institutional Repository, 1999. http://repository.hkbu.edu.hk/etd_ra/182.
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Beitat, Alexander [Verfasser]. "Investigations on the behavior of zinc and copper complexes containing polydentate amine ligands / Alexander Beitat". Gießen : Universitätsbibliothek, 2012. http://d-nb.info/1064990703/34.
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Ward, Benjamin D. "New chemistry of Groups 3 and 6 transition metals supported by polydentate N-donor ligands". Thesis, University of Oxford, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.269802.
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Riis-Johannessen, Thomas. "The synthesis and structural characterisation of metallosupramolecular complexes based on neutral polydentate N-donor ligands". Thesis, University of Bristol, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.432965.
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Fennessy, Rebecca Valerie. "Synthesis of polydentate ligands and their self-assembly into helicates, meso-helicates and cyclic helicates". Thesis, University of Huddersfield, 2013. http://eprints.hud.ac.uk/id/eprint/23326/.
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Described here is the synthesis and coordination chemistry of various ligands, L1 – L17. Some of the ligands presented form interesting supramolecular assemblies upon reaction with selected metal ions. Chapter 1 provides a general introduction to supramolecular chemistry and self-assembly. Chapter 2 introduces a new class of potentially hexadentate symmetrical ligands, L1 – L5. These ligands consist of two tridentate binding sites separated by a 1,3-phenylene spacer unit. Reaction of L1 with Zn(II) ions results in the formation of a pentanuclear circular helicate [Zn5(L1)5]10+, within the structure all five zinc ions are six-coordinate arising from coordination of two tridentate domains from two different ligand strands. This structure was shown to exist in both the solid state and in solution. Incorporation of various enantiopure units allowed variation of the terminal functional group of the ligand, L2 – L5. These ligands, upon coordination with Zn(II) ions, were shown to from supramolecular assemblies analogous to the pentanuclear species observed for L1. Additionally these ligands were shown to be diastereoselective, controlling the resulting supramolecular architecture giving up to 80% diastereomeric excess. Described in Chapter 3 are a number of potentially hexadentate N-donor ligands, L6 – L14. Each ligand possesses the same thiazole-pyridyl-pyridyl tridentate domains, with variation of the spacer unit. Upon coordination with selected transition metal ions these ligands resulted in the formation of dinuclear species. Reaction of L9 with Cd(II) results in the formation of a dinuclear double helicate, in which the two tridentate domains coordinate each metal ion and the ligands twist in the centre generating an ‘over and under’ arrangement. However, reaction of L9 with Co(II) results in the formation of a dinuclear meso-helicate, in which the ligands adopt a side-by-side configuration. This difference in structure is attributed to unfavourable steric interactions which prevent the formation of the Co(II) double helicate. Reaction of two of these ligands L10, which possesses an ethylene glycol chain, and L11, containing an amine group, with Cd(II) and camphorsulfonic acid results in the formation of a heteroleptic one-dimensional chain. Hydrogen bonding interactions between the protonated amine of L11 and the glycol chains of L10 results in a structure which contains both of these meso-helicate structures in an extended one-dimensional arrangement (([Cd2(L10)2][Cd2(L11-H)2])(ClO4)10)n. Chapter 4 reports the synthesis of three ligands, L15 – L17, each containing the same central phenol unit, and either a hydroxyl, pyridine or pyridine-N-oxide terminal unit. Reaction of each ligand with various trivalent lanthanide ions results in the formation of a dinuclear double helicate. In each structure the central phenol unit is deprotonated and bridges the two lanthanide ions giving [L2M2]4+. L17, which possesses the pyridine-N-oxide as the terminal group, effectively encompasses the cations minimising access for the coordination of any anions or solvent molecules. Photophysical measurements show that this ligand forms emissive complexes with a number of lanthanide ions, whilst the magnitude of the lifetime for [(L17)2Yb2]4+ (= 21.0 s) suggests that both Yb(III) ions are well-shielded from excited state quenching phenomena.
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Mishra, Dipu Kumar. "Some novel transition metal complexes of polydentate ligands: synthesis, physico-chemical characterization and DNA Interaction study". Thesis, University of North Bengal, 2021. http://ir.nbu.ac.in/handle/123456789/4759.
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陳凱珊 y Hoi-shan Chan. "Syntheses, reactivity and coordination chemistry of d10 metal complexes of phosphorus and nitrogen donating polydentate ligands". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1999. http://hub.hku.hk/bib/B31220368.
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Dubé, Tiffany. "Organometallic transformations of di- and trivalent samarium supported by polydentate macrocyclic ligands: Low-valent samarium complexes of di- and tetrapyrrole ligand systems". Thesis, University of Ottawa (Canada), 2000. http://hdl.handle.net/10393/8652.
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SmI2(THF)5 acted as a reducing agent in the reaction with phenylenebis(3,5-But4salicylidene)iminato sodium, (3,5-But4salophen)Na2(THF) 2, to yield a dimeric compound [Sm2(SB-SB)(THF)3] ·2toluene (2.2) [SB-SB = C-C bonded (3,5-Bu t4salophen dimer] arising from the reductive C-C coupling of two imine functional groups of two (3,5-But4salophen)Sm units. Complex 2.2 reacts with MeLi resulting in a novel oxo-bridged dimer, {[(Me2-SB)Sm(mu-CH3)Li(THF)][(Me2-SB)Sm(mu-CH 3)Li(THF)2Li(TBT)2]}(mu-O)(mu-Li)3 (2.3) [Me2SB = phenylenebis (3,5-But 4salicyl)dimethyldiamidato], featuring alkylation of both Sm atoms and arising from cleavage of the C-C bond connecting the two units, as well as complete reduction of the imine groups of the two salophen ligands and TBF deoxygenation. Similar cleavage of the connecting C-C bond of complex 2.2 was also observed during the reaction with dry O2 to form a distorted cuboid cluster in which four Sm atoms are bridged by four hydroxyl groups [(3,5-But4salophen)Sm (OH)] 4·4toluene (2.4). The nature of the substituents present on the calix-tetrapyrrole tetra-anion ligand {[R2C(C4H2N)]4} 4- [R = 1/2-(CH2)5- (a), Et (b)] determines the type of reactivity of the corresponding Sm(II) compounds with acetylene. Where R = 1/2-(CH2)5- dehydrogenation occurred to yield the nearly colorless dinuclear diacetylide complex. Conversely, where R = Et, acetylene coupling in addition to dehydrogenation resulted in the formation of a dimeric butatrienediyl enolate derivative. Reaction of the trivalent hydride or of the terminally bonded methyl derivative with acetylene resulted in a mixture of the carbide and the dimerization product 5.2b. The same reaction also yielded a third product, a trivalent complex in which the macrocycle was isomerized by shifting the ring attachment of one of the four pyrrole rings. Reaction of the mononuclear and trivalent (6.1a), ( 6.1b) with lithium under Ar in THF afforded the mononuclear divalent 6.3a where the enolate was formed by a THF cleavage process. In the case of direct reaction of SmI2(THF)5 with the tetralithiated form of the Rn-calix-pyrrole ligand, the two isomorphous enolates (6.3a and 6.3b) were the only isolated products. Complexes 6.3 react reversibly with ethylene to afford the corresponding light-green dinuclear ethylene adducts. The nature of the substituents; present on a dipyrrolide dianion ligand determines the assembly of Sm(II) clusters which participate to various extents in dinitrogen fixation and THF cleavage. Reaction of SMI2(THF) 2 with the methylphenyl dipyrromethanyl dianion resulted in the pentameric cluster 10.1 which exhibited no reactivity with dinitrogen. Conversely, reaction of SmI2(THF)2 with the cyclohexyl dipyrromethanyl dianion resulted in TBF cleavage to yield the tetranuclear oxo-bridged complex 10.2. (Abstract shortened by UMI.)
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Dube, Tiffany Lynn. "Organometallic transformations of di-and trivalent samarium supported by polydentate macrocyclic ligands, low-valent samarium complexes of di-and tetrapyrrole ligand systems". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0020/NQ57037.pdf.
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Ellis, David. "A study of stereochemical non-rigidity in organometallic and co-ordination complexes of polydentate chalcogen containing ligands". Thesis, University of Exeter, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.279766.
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Straistari, Tatiana. "Synthesis and study of coordination compounds of cobalt, copper, palladium and nickel with polydentate ligands containing sulfur". Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4352.
Texto completoResumen
Ce travail porte sur la synthèse, la caractérisation et l’évaluation en catalyse de réduction des protons en dihydrogène, de nouveaux complexes de Ni(II), Co(III), Cu(II) et Pd(II) basés sur des ligands de type thiosemicarbazone. La nature de l’espèce catalytique active a été étudiée par voltampérométrie cyclique et des propositions de mécanisme ont été formulés sur la base de calcul quantique de type DFT.Le premier chapitre introduit le contexte scientifique. Le second chapitre concerne la synthèse et la caractérisation des ligands de type N2S2 et des complexes mononucléaires associés de Ni, Cu et Pd. Le troisième chapitre présente la synthèse et la caractérisation de complexes binucléaires de Co et trinucléaire de Ni.Les études électrochimiques de ces complexes dans le DMF en présence d’une source de protons, nous a permis d’évaluer leur efficacité catalytique. Nos résultats montrent que les complexes du Cu et du Pd présentent une vague irréversible spécifique pour la réduction des protons, mais une décomposition est observée durant l’électrolyse. Par contre, les complexes de Ni et de Co ont montré une stabilité électrochimique ainsi que de bonnes performances catalytiques. En particulier, le nouveau complexe mononucléaire de Ni présente des propriétés catalytiques remarquables qui le classent parmi les meilleurs catalyseurs de la réduction des protons décrits dans la littérature. L’ensemble de ce travail fourni une description complète du comportement électrochimique des ligands de type N2S2 complexés à des métaux de transition. Il permet d’envisager des développements futurs dans l’amélioration des propriétés catalytiques de ces complexesThis work focuses on the synthesis, the characterization and the catalytic evaluation in the reduction of protons into dihydrogen, of new complexes of Ni(II), Co(III), Cu(II) and Pd(II) based ligands Type thiosemicarbazone. The catalytically active species during the process of the proton reduction was studied by cyclic voltammetry and mechanisms were formulated on the basis quantum chemical calculation.The first chapter introduces the scientific context, the goals and the main objectives of this work. The second chapter concerns the synthesis and the characterization of the N2S2 ligands and their associated mononuclear complexes, Ni, Cu and Pd. The third chapter presents the synthesis and the characterization of binuclear Co and trinuclear Ni based on N2S2 ligand.Electrochemical studies of these complexes in DMF in the presence of a proton source (trifluoroacetic acid), allowed us to evaluate their catalytic efficiency. Our results show that Cu and Pd complexes have a specific irreversible wave for the reduction of protons, but decomposition is observed during electrolysis, which makes these uninteresting complexes for the reduction of protons.On the contrary, Ni and Co complexes showed an electrochemical stability and good catalytic performances. In particular, the new mononuclear Ni complex exhibits remarkable catalytic properties that rank it among the best catalysts for the reduction of protons reported in the literature. All this work provided a complete description of the electrochemical behavior of N2S2 thiosemicarbazone ligands complexed to transition metals. It allows considering future developments in improving the catalytic properties of these complexes
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Liang, Hongze. "Synthesis, crystal structures and spectroscopic properties of mono- and bi-metallic Schiff-base complexes ; Synthesis of polydentate and macrocyclic phosphine ligands, and their reactivities towards transition and lanthanide metal ions". HKBU Institutional Repository, 2001. http://repository.hkbu.edu.hk/etd_ra/294.
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Carmo, dos Santos Nadia A. "Syntheses and application of nitrogen based polydentate ligand complexes". Doctoral thesis, Università degli studi di Padova, 2017. http://hdl.handle.net/11577/3427281.
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This Ph.D. thesis describes the versatility of metal complexes with tris(2-pyridylmethyl)amine (TPMA) based ligands to be used either as self-assembling molecular scaffolds with application on molecular recognition and chiroptical probing, or as active catalysts in atom transfer radical polymerization and hydrogen evolving catalysis reactions. Quantitative chirality determination is fundamental due to the broad effect that stereochemistry has in many different scientific fields. Within this subject, there is a strong urge to develop fast and effective methods to perform stereochemical analysis to couple with high throughput screening methods for production or analysis of biological samples. Chiroptical methods are able to provide the speed and accuracy that enantiomeric excess determination measurement needs. Within that scope, three molecular probes for amino acids have been developed allowing to perform enantiomeric determination and absolute configuration by measuring the induced circular dichroism (CD), vibrational circular dichroism (VDC) or circularly polarized luminescence (CPL). The reported systems were able to provide reliable information about the chirality of the studied analytes.
In this dissertation the mechanistic investigation for the elucidation of the self-assembly process of TPMA with amino acids and metals is described. The complex equilibrium that yields the dimeric supramolecular architectures responsible for the chiroptical signals is exposed. The main factor that affects the final products of the reaction as well. Then the effects on the chiroptical response when changing the metal ions on the main structure are reported. Some impressive results were obtained by using Co (II) instead of Zn (II) on the VCD measurements. It was actually possible to enhance the signal intensity by two orders of magnitude. Furthermore, after modifying the initial ligand structure to add a quinolinic moiety in order to give fluorescent properties to the system, it was possible to obtain CPL bands.
Moreover, the versatility of the studied ligands was assessed in other areas like catalysis. Eight novel copper complexes were synthesized and applied as active catalysts in atom transfer radical polymerization (ATRP). Hidroxyquinolinic based cobalt, nickel and iron complexes were evaluated as potential catalysts for hydrogen evolving reactions with positive results.Questa tesi di dottorato descrive la versatilità dei complessi metallici con leganti tris(2-piridilmetil)amminici (TPMA) da utilizzare come scaffold molecolari autoassemblanti con applicazione sul riconoscimento molecolare e sonde chiroptiche, o come catalizzatori attivi nella polimerizzazione radicale a trasferimento atomico e reazioni di catalisi di sviluppo di idrogeno. La determinazione quantitativa della chiralità è fondamentale a causa dell'ampio effetto che la stereochimica ha in molti campi scientifici diversi. All'interno di quest’area, esiste una grande necessità di sviluppare metodi rapidi ed efficaci per eseguire analisi stereochimiche da abbinare a metodi di screening ad alto rendimento per la produzione o l'analisi di campioni biologici. I metodi chiropici sono in grado di fornire la velocità e la precisione necessarie per la determinazione dell’eccesso enantiomerico. Con questo obiettivo sono state sviluppate tre sonde molecolari per amminoacidi che consentono di eseguire la determinazione enantiomerica e la configurazione assoluta misurando il dicroismo circolare indotto (CD), il dicroismo circolare vibrazionale (VDC) o la luminescenza circolare polarizzata (CPL). I sistemi riportati sono stati in grado di fornire informazioni affidabili sulla chiralità degli analiti studiati. In questa dissertazione viene descritta l'indagine meccanicistica per la delucidazione del processo di auto-assemblaggio di TPMA con amminoacidi e metalli. Viene esposto il complesso equilibrio che produce le architetture supramolecolari dimeriche responsabili dei segnali chiropici. Il fattore principale che influisce anche sui prodotti finali della reazione. Quindi vengono riportati gli effetti sulla risposta chiropica al cambiare degli ioni metallici sulla struttura principale. Alcuni risultati significativi sono stati ottenuti utilizzando Co (II) invece di Zn (II) sulle misurazioni VCD. In realtà è stato possibile aumentare l'intensità del segnale di due ordini di grandezza. Inoltre, dopo aver modificare la struttura del legante iniziale per aggiungere un gruppo chinolinico al fine di conferire proprietà fluorescenti al sistema, è stato possibile ottenere le bande CPL. In aggiunta, la versatilità dei leganti studiati è stata valutata in altre aree come la catalisi. Otto nuovi complessi di rame sono stati sintetizzati e applicati come catalizzatori attivi nella polimerizzazione radicale a trasferimento atomico (ATRP). I complessi cobalto, nichel e ferro idrossichinolinici sono stati valutati come potenziali catalizzatori per reazioni di sviluppo di idrogeno con risultati positivi.
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WASCHBUSCH, KLAUS. "Synthese et chimie de coordination de ligands bi- et polydentates comportant des sous-unites phosphinines". Palaiseau, Ecole polytechnique, 1997. http://www.theses.fr/1997EPXX0001.
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Les ligands phosphinines, presentant un fort pouvoir -accepteur, sont particulierement bien adaptes a la stabilisation des centres metalliques riches en electrons. Nous avons etudie de facon approfondie la synthese de ligands mixtes comportant a la fois des sous-unites phosphinines et phosphines. Deux voies d'acces a ces nouveaux types de ligands ont ete developpees : - le couplage-croise entre les 2-bromophosphinines et l'anion phospholyllithium, catalyse par les complexes du nickel ou du palladium, permet l'obtention des 2-phospholyl-phosphinines. Ces dernieres sont de remarquables precurseurs de di- et polyphosphines chelatantes. (deuxieme partie) - la condensation du tribromure de phosphore avec la 2-bromo-4,5-dimethylphosphinine permet la preparation de la 2-dibromophosphino-4,5-dimethylphosphinine. Celle-ci est un synthon ideal pour l'elaboration de 2-phosphino-phosphinines fonctionnelles et de polyphosphines. (troisieme partie) a la fin de chaque partie, une etude preliminaire de la chimie de coordination de ces nouveaux ligands est presentee.
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Stollberg, Peter. "Synthesis and Characterization of Polydentate C3 Symmetric Ligand Systems in Metal Coordination". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2018. http://hdl.handle.net/21.11130/00-1735-0000-0003-C119-7.
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Steczek, Lukasz. "Complexation of actinides Am(III), Th(IV), Pu(IV) and U(VI) with poly-N-dentate ligands SO3-Ph-BTP and SO3-Ph-BTBP". Thesis, Montpellier, 2016. http://www.theses.fr/2016MONTT238/document.
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La complexation des ions Th(IV), U(VI), Am(III) et Pu(IV) avec le ligand hydrophile SO3-Ph-BTP4- et des ions Th(IV) et Pu(IV) avec le ligand hydrophile SO3-Ph-BTBP4– a été étudiée. Ces nouveaux ligands ont été proposés dans le cadre du recyclage des combustibles nucléaires usés, pour la séparation sélective d’actinides(III) par rapport aux lanthanides(III) et aux produits de fission. L’objectif de ce travail était d’étudier la capacité de ces ligands à complexer les actinides de degré supérieur, soit IV et VI. Après des essais infructueux par spectroscopie directe, la méthode appliquée pour atteindre cet objectif est une étude par extraction liquide-liquide. Le système d'extraction est composé de deux ligands chélatants qui sont en compétition pour complexer les ions actinides: l’extractant tétraoctyldiglycolamide (TODGA), molécule neutre, lipophile, donneur oxygéné tridenté et le complexant anionique hydrophile tridenté (ou tétradenté) SO3-Ph-BT(B)P4–. La méthode consiste à mesurer l’évolution de l’extraction du cation par le TODGA (DM) lors de l’ajout de quantité croissante de complexant en phase aqueuse, tout en fixant une force ionique constante en phase aqueuse. Un modèle mathématique est établi en prenant en compte les équilibres d’extraction et de complexation, il permet d’évaluer la stœchiométrie des complexes formés et leurs constantes de stabilité relatives. Les expériences réalisées ont permis de conclure à la présence des complexes An:SO3-Ph-BTP4– 1:1 et 1:2 pour tous les actinides testés et du complexe 1:1 pour An(IV):SO3-Ph-BTBP4–.Deux séries de constantes conditionnelles de stabilité de ces complexes ont été déterminées dans nos expériences: des constantes de stabilité conditionnelles, αL,i, valables pour une solution 1 M en nitrate et faciles à évaluer et des constantes ßL,i, considérant de manière explicite la complexation des cations par les nitrates, toujours pour une force ionique I = 1 M. En considérant les constantes conditionnelles de stabilité ßL,i, des actinides pour les ligands SO3-Ph-BTP4- et SO3-Ph-BTBP4-, l'ordre suivant est observé: UO22+ < Am3+ < Th4+ < Pu(IV), conformément à l’augmentation du potentiel ionique z/r2, où z est la charge formelle et r est le rayon de l'ion métallique. L'analyse des valeurs ßL,i suggère que les effets électrostatiques jouent un rôle plus important dans la formation des complexes entre les ligands azotés polydentés et les ions actinide.Pour les complexes de Am3+ avec le ligand SO3-Ph-BTP4– tridenté, si on compare nos résultats avec l’étude menée par TRLFS (fluorescence laser à résolution temporelle) pour des complexes analogues de Cm3+, les constantes de stabilité de stoechiométrie 1:1 et 1:2, déterminées par extraction liquide-liquide sont plus faibles. En outre, la stœchiométrie 1:3 décrite pour Cm3+ n'a pas été détectée dans notre étude. Les constantes de stabilité des complexes SO3-Ph-BTP et SO3-Ph-BTBP avec les actinides(IV) n'ont pas été rapportées dans la littérature. Néanmoins les complexes supérieurs n’ont pas été observés: 1:3 avec le ligand tridenté SO3-Ph-BTP4– et 1:2 avec le ligand tétradenté SO3-Ph-BTBP4–. Ces observations surprenantes à priori peuvent provenir du traitement mathématique simplifié des équilibres chimiques et nécessiteraient des vérifications supplémentaires par des techniques permettant d’identifier les complexes en solution. Cependant, les données de partage obtenues ont permis de proposer des constantes de stabilité conditionnelles qui peuvent être exploitées pour modéliser le comportement des actinides (III), (IV) et (VI) dans un procédé de séparationThe complexation of Th(IV), U(VI), Pu(IV) and Am(III) with the hydrophilic ligand SO3-Ph-BTP4–, and of Th(IV) and Pu(IV) with the hydrophilic SO3-Ph-BTBP4– ligand was studied. These new hydrophilic aromatic poly-N-dentate ligands are proposed, in the frame of recycling spent nuclear fuel, for a selective separation of actinides(III) from lanthanides(III) and from other fission products. The aim of this work was to compare the ability of the actinide ions to coordinate these N-dentate molecules. After some disappointing tests with classical spectroscopies, the method of liquid-liquid (solvent) extraction was applied to reach this goal. The extraction system consisted of two chelating ligands that competed for the actinide ions: a lipophilic tri-O-dentate neutral molecule of dioctylamide (TODGA) and a hydrophilic tri(or tetra)-N-dentate anion SO3-Ph-BT(B)P4–. The simple model we applied, well known in literature, considered chemical equilibria resulting in accumulation of the metal complexes with the lipophilic ligand in the organic phase, and those with the hydrophilic ligand – in the aqueous phase. With increasing concentration of the hydrophilic ligand (the concentration of the lipophilic ligand being constant) the equilibrium shifted towards the complexes with the hydrophilic ligand, and the distribution ratio of the metal decreased.The results have been interpreted in terms of the formation of 1:1 and 1:2 actinide complexes with tridentate SO3-Ph-BTP4– and only single 1:1 An(IV) complexes with tetradentate SO3-Ph-BTBP4– ligands in the two-phase systems studied. Two series of conditional stability constants of the complexes have been determined in our experiments: one set of the conditional stability constants, αL,i, related to 1 M nitrate media, whereas the other, βL,i, – to aqueous solutions of ionic strength I = 1 M, where the complexation by nitrates was taken into account. In the latter case, when the effect of the actinide complexation by nitrates was deducted, the conditional stability constants, βL,1, of the actinide complexes with SO3-Ph-BTP4– increase in the order UO22+ < Am3+ < Th4+ < Pu(IV), in accordance with the increasing z/r2 ratio (where z is the formal charge and r is the radius of the metal ion). The analysis of the βL,i values suggests that the electrostatic effects play the major role in the formation of the complexes between the poly-N-dentate ligands and actinides ions.Concerning the complexation of Am3+ with the tri-N-dentate SO3-Ph-BTP4– ligand, if we compare our results with the literature values for the analogous Cm3+ complexes studied by a spectroscopic (TRLFS) technique, the stability constants of 1:1 and 1:2 complexes of Am3+ are much lower, and its 1:3 complex has not been found by the solvent extraction method. The stability constants of the SO3-Ph-BTP and SO3-Ph-BTBP complexes with the actinides(IV) have not been reported yet in literature, therefore such comparison was impossible in this case. However, the expected 1:3 complexes of Pu(IV) and Th(IV) with the SO3-Ph-BTP4– ligand have not been found in our solvent extraction experiments as well. Similarly, only 1:1 Pu and Th complexes with the tetra-N-dentate SO3-Ph-BTBP4– ligand have been found by solvent extraction, in spite of that the 1:2 complexes were also expected. These surprising results could be a result of oversimplification of the used model of extraction, and should be completed by further spectroscopic studies to identify all the complexes formed in the two-phase system studied. Nevertheless, the stability constants determined in the solvent extraction experiments (“practical” stability constants) allow us to correctly describe and to predict the behaviour of metal ions in such two-phase systems
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Grimaldo, Morón José Teófilo. "Contribution à la synthèse de macrocycles tétraphosphorés : ligands polydentates présentant un intérêt biomédical". Grenoble 1, 1987. http://www.theses.fr/1987GRE10161.
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Synthese de ligands macrocycles tetraphores, complexants potentiels de cations paramagnetiques (gd**(3+), fe**(3+)) et de nucleide radioactifs. Etude de la reactivite de ces ligands et des essais de complexation
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Grimaldo, Morón José Teófilo. "Contribution à la synthèse de macrocycles tétraphosphorés ligands polydentates présentant un intérêt biomédical /". Grenoble 2 : ANRT, 1987. http://catalogue.bnf.fr/ark:/12148/cb376056754.
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SAVA, XAVIER. "Synthese et chimie de coordination de ligands mono- et polydentates a base d'unites phosphaferrocene". Palaiseau, Ecole polytechnique, 2000. http://www.theses.fr/2000EPXX0036.
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Les phosphaferrocenes sont les analogues phosphores des ferrocenes. Dans le premier chapitre nous rappelons les proprietes electroniques et chimiques de ces composes, leurs principales voies d'acces, ainsi que les differents exemples de complexation aux metaux de transition recenses dans la litterature. Au cours du chapitre ii, la synthese de phosphaferrocenes fonctionnalises et la construction de polydentes a base d'unites phosphaferrocenes sont presentees. Nous pouvons mentionner la synthese d'un phosphaferrocene-oxazoline, optiquement actif, et celle d'un tridente mixte phosphaferrocene-phosphinines, obtenu par couplage d'alcynes au zirconium. Le chapitre suivant (chap. Iii) aborde la chimie de coordination des mono- et diphosphaferrocenes. Ces composes se coordinent aux metaux de transition via un atome de phosphore hybride sp 2. Les complexes formes permettent d'obtenir diverses informations quant aux proprietes electroniques de ces ligands, et mettent en evidence la richesse et l'originalite de leurs modes de coordination. Des structures de type chelate, une coordination mu 2 du phosphore, et des liaisons datives du fer vers un palladium(i) ont notamment ete observees. Le chapitre iv presente des applications des complexes de phosphaferrocenes en catalyse d'hydroformylation et de couplage croise de suzuki. Dans ce dernier cas, de tres fortes activites sont obtenues, vraisemblablement grace au caractere hemilabile de la complexation des diphosphaferrocenes au palladium. Enfin le dernier chapitre aborde l'etude de l'oxydation des phosphaferrocenes, avec la caracterisation des premiers mono- et diphosphaferroceniums. Des calculs dft apportent des informations complementaires quant a la structure electronique des phosphaferrocenes et a leurs proprietes coordinatives originales.
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Wagner, Thomas Helmut Verfasser], Andreas [Akademischer Betreuer] [Grohmann y Berthold [Akademischer Betreuer] Kersting. "Polydentate Liganden des Calix[4]arens / Thomas Helmut Wagner. Gutachter: Andreas Grohmann ; Berthold Kersting. Betreuer: Andreas Grohmann". Berlin : Technische Universität Berlin, 2013. http://d-nb.info/1067384510/34.
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Wagner, Thomas Helmut [Verfasser], Andreas [Akademischer Betreuer] Grohmann y Berthold [Akademischer Betreuer] Kersting. "Polydentate Liganden des Calix[4]arens / Thomas Helmut Wagner. Gutachter: Andreas Grohmann ; Berthold Kersting. Betreuer: Andreas Grohmann". Berlin : Technische Universität Berlin, 2013. http://d-nb.info/1067384510/34.
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Gentschow, Simon-Andreas Verfasser] y Andreas [Akademischer Betreuer] [Grohmann. "Koordinationsverhalten polydentater N1Pn-Liganden (n = 1 - 4) [[Elektronische Ressource]] / Simon-Andreas Gentschow. Betreuer: Andreas Grohmann". Berlin : Universitätsbibliothek der Technischen Universität Berlin, 2011. http://d-nb.info/1018072780/34.
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Gachot, Grégory. "Synthèses et étude de la coordination à des métaux de nouveaux ligand électroactifs : les tétrathiafulvalènythioalkylphosphines mono ou polydentates". Rennes 1, 2005. http://www.theses.fr/2005REN1S044.
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L’objectif de ce travail est l’étude de nouveaux tétrathiafulvalène-thioalkylphosphines et leur utilisation en tant que ligands électroactifs pour l’élaboration de molécules hybride organique-inorganiques. Nous décrivons les synthèses de TTF mono, di et tétrasubstitués possédant des espaceurs alkylthio entre le cœur TTF et la fonction phosphine, ainsi que leur coordination à des complexes métalliques. Nous avons mis en évidence la versatilité du ligand TTF thioalkylmonophosphine qui peut agir comme un ligand mono (P) ou bidentate (P,S). Des TTF cyclophanes comportant un métal par cycle ont également été préparés à partir des TTF diphosphines. Des essais de formation de complexes par transfert de charge à partir de ces mêmes TTF cyclophanes sont décris. Nous présentons également la synthèse de TTF biscyclophanes dont il a été possible de contrôler la formation de chaque cycle soit latérale au cœur TTF soit à chaque extrémité des dithioles.
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Belhadj-Tahar, Abdel Hafid. "Complexes du technétium-99 et du rhénium avec de nouveaux ligands polydentates dérivés de l'acide dithiocarboxylique : développement de radiopharmaceutiques oxo et nitrurotechnétiés pour l'évaluation des débits sanguins régionaux". Université Joseph Fourier (Grenoble), 1996. http://www.theses.fr/1996GRE10001.
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Les travaux presentes dans ce memoire s'inserent dans un projet pluridisciplinaire (chimie de coordination, radiochimie et medecine) visant a la mise au point de nouveaux radiopharmaceutiques oxo- et nitruro-techneties utilisables pour l'evaluation des debits sanguins locaux. Dans la premiere partie, l'auteur rend compte de la synthese et la caracterisation de nouveaux ligands vecteurs polydentes derivant de l'acide aminocyclopentene-dithiocarboxylique et susceptibles d'offrir au metal differentes combinaisons de sites donneurs s#mn#no#o. Dans la deuxieme partie sont decrites les protocoles de marquage de ces ligands par des curs oxo et nitruro renfermant l'isotope technetium-99m. La structure de certains des complexes obtenus a pu etre confirmee par comparaison a celle de complexes homologues du rhenium et du technetium-99 (a periode longue). Ces chelates ont montre une stabilite remarquable dans les conditions physiologiques et une liposolubilite convenable pour permettre une extraction facile et une bonne diffusion tissulaire. La troisieme partie rend compte des etudes de biodistribution realisees chez le rat. Il apparait que d'une maniere generale les complexes neutres nitruro presentent un bon taux de fixation sur le cur alors que ceux ayant un caractere acido-basique se fixent selectivement sur les reins. La contribution des differents facteurs (lipophilie, fixation sur les proteines et globulaire) conditionnant la biodistribution est evaluee et discutee dans la derniere partie
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Stollberg, Peter [Verfasser], Dietmar [Akademischer Betreuer] Stalke, Dietmar [Gutachter] Stalke, Sven [Gutachter] Schneider, Ulf [Gutachter] Diederichsen, Christian [Gutachter] Sindlinger, Franziska [Gutachter] Thomas y Heidrun [Gutachter] Sowa. "Synthesis and Characterization of Polydentate C3 Symmetric Ligand Systems in Metal Coordination / Peter Stollberg ; Gutachter: Dietmar Stalke, Sven Schneider, Ulf Diederichsen, Christian Sindlinger, Franziska Thomas, Heidrun Sowa ; Betreuer: Dietmar Stalke". Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://d-nb.info/1188025163/34.
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Herber, Ulrich Verfasser], Sonja [Akademischer Betreuer] [Herres-Pawlis y Jun [Akademischer Betreuer] Okuda. "From Ligand Design to Lactide Polymerisation Catalysis -A study on novel polydentate bis(pyrazolyl)methanes and their Fe(II), Cu(II) and Zn(II) complexes / Ulrich Herber ; Sonja Herres-Pawlis, Jun Okuda". Aachen : Universitätsbibliothek der RWTH Aachen, 2017. http://d-nb.info/1162499575/34.
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Mabad, Bouchra. "Modelisation du site d'oxydation de l'eau en photosynthese : complexes du manganese avec des bases de schiff polydentees". Toulouse 3, 1987. http://www.theses.fr/1987TOU30103.
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Lee, Chang-Tai y 李長泰. "Quadruply Bonded Complexes Containing Polydentate Ligands". Thesis, 1996. http://ndltd.ncl.edu.tw/handle/93810891732065305351.
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Wu, Ying-Yann y 吳英彥. "Dimolybdenum Complexes Containing Polydentate Nitrogen Ligands". Thesis, 2002. http://ndltd.ncl.edu.tw/handle/40861862709701438435.
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Yang, Pang-Yen y 楊邦彥. "Chemistry of transition metal Complexes Containing Polydentate Ligands". Thesis, 2001. http://ndltd.ncl.edu.tw/handle/71159509299058578672.
Texto completoResumen
碩士中原大學
化學研究所
89
ABSTRACT This thesis discusses the chemistry of transition metal complexes containing polydentate ligands. The complex W(CO)4(HDpyF), 1, was prepared by reaction of W(CO)6 with HDpyF (HDpyF = N,N’-di(2-pyridyl)formamidine) in THF. The spectroscopic data of 1 has been recorded and the structure of 1 determined by X-ray crystallography. Crystal data for 1: space group Pī, a = 7.319 (1) Å, b = 9.788(1) Å, c = 12.094 (1) Å, □ = 79.901(1)º, □ = 79.243(1)º, □ = 69.497(1)º, V = 791.55(11) Å3, and Z = 2, with final residuals R = 0.0243 and Rw = 0.0648. The complex W(CO)4(HDMPyF), 2, was prepared by reaction of W(CO)6 with HDMpyF (HDMpyF = N,N’-di[2-(6-methyl-pyridyl)]formamidine) in Toluene. The spectroscopic data of 2 has been recorded and the structure of 2 determined by X-ray crystallography. Crystal data for 2: space group Pī, a = 7.1840(9) Å, b = 10.132(2) Å, c = 13.276(2) Å, □ = 79.877(9)º, □ = 80.251(11)º, □ = 72.116(13)º, V = 898.5(2) Å3, and Z = 2, with final residuals R = 0.0489 and Rw = 0.1291. The HDPyF and HDMpyF ligands in complexes 1 and 2 were coordinated to the metal centers in novel bidentate fashions. Complexes 1 show supramolecular structure in the solid state by intermolecular hydrogen bonds and aromatic □□□ stacking interactions. Complexes 2 shows supramolecular structure in the solid state through aromatic □□□ stacking interactions. The complex Co(dipm)(NO3)2(CH3OH), 3, and Cu(dipm)(NO3)2(CH3OH), 4, were prepared by reaction of Co(NO3)2·6H2O and Cu(NO3)2·6H2O, respectively, with dipm (dipm = dipyridylamine) in CH3OH. The spectroscopic data of 3 and 4 have been recorded and the structure of 3 and 4 determined by X-ray crystallography. Crystal data of 3: space group Pī, a = 6.959(1) Å, b = 7.353(1) Å, c = 14.667(1) Å, □ = 84.261(6)º, □ = 80.292(6)º, □ = 81.086(7)º, V = 728.69(10) Å3, and Z = 2, with final residuals R = 0.0248 and Rw = 0.0639. Crystal data of 4: space group Pī，a = 7.306 (1) Å, b = 7.373 (1) Å, c = 13.896(2) Å, □ = 95.225(8)º, □ = 94.396(9)º, □ = 98.998(9)º, V = 733.10(14) Å3, and Z = 2, with final residuals R = 0.0691 and Rw = 0.1602。The dipm ligand in complexes 3 and 4 were coordinated to the metal centers in novel bidentate fashions. Complexes 3 and 4 show dimeric structure in the solid state through multiple N-H---N and C-H---N intermolecular hydrogen bonds. The new ligand S-6-Amino-2-(2-methylbutylsulfanyl)-pyrimidine-4-one (S-HAmbspo), 5, was prepared by reaction of 4-Amino-6-hydroxy-mecaptopyrimidine monohydrate with p-Tolnnenesulfonic Acid S-2-methylbutyl Ester and K2CO3 in DMF. The ligand 6-Amino-2-methysulfanyl-3H-pyrimidine-4-one (HAmspo), 6, was prepared by reaction of 4-Amino-6-hydroxy-mecaptopyrimidine monohydrate with p-Tolnnenesulfonic Acid methyl Ester and K2CO3 in DMF. Their spectroscopic data and Mass spectra have been recorded and their structures have been determined by X-ray crystallography. Crystal data for 5: space group R3, a = b = 30.249(2) Å, c = 7.275(1) Å, □ = 120º, V = 5765.1(6) Å3, and Z = 16, with final residuals R = 0.0468, and Rw = 0.1234. Crystal data for 6: space group P21/n, a =11.059(2) Å, 10.998(2) Å, 11.775(2)Å, □ = 99.885(2)º, V = 1410.8 Å3, and Z = 8, with final residuals R = 0.0576 and Rw = 0.1188. Complexes 5 and 6 show supramolecular structure in the solid state by intermolecular hydrogen bond and aromatic □□□ stacking interactions. The quadruply bonded complex Mo2(S-Ambspo)4, 7, was prepared by reactions of Mo2(OAc)4 with S-HAmbspo in CH3CN. Its spectroscopic data have been recorded and the structure has been determined by X-ray crystallography. The complex Cu(S-HAmbspo)3(NO3)2, 8, was prepared by reactions of Cu(NO3)2·6H2O with S-HAmbspo in THF. Its spectroscopic data have been recorded and the structure has been determined by X-ray crystallography. Crystal data for 8: space group I4(1), a = 15.6604(7) Å, b = 15.6604(7) Å, c = 19.1990(12) Å, V = 4708.5(4) Å3, and Z = 4, with final residuals R = 0.0493 and Rw = 0.1526. Crystal data for 8: space group P1, a = 8.560(1) Å, b = 16.055(1) Å, 17.199(1) Å, □ = 93.982(1)º, □ = 92.331(1)º, □ = 97.608(1), V = 2334.0(2) Å3, and Z = 2, with final residuals R = 0.0766 and Rw = 0.2107. The S-Ambspo ligand coordinates to the metal centers through one amine nitrogen atom and one pyrimidine nitrogen atom. Its effect on the optical activity of the Mo24+ unit is discussed. Complex 8 also shows supramolecular structure in the solid state by intermolecular hydrogen bond and aromatic □□□ stacking interactions.
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Yen, Yung-Sheng y 嚴詠聖. "Chemistry of Transition Metal Complexes Containing Polydentate Nitrogen Ligands". Thesis, 2001. http://ndltd.ncl.edu.tw/handle/19726124986479543651.
Texto completoResumen
碩士中原大學
化學研究所
89
The complex cis-[Mo2(HDpyF)2(CH3CN)4][BF4]4, 1, was prepared by reaction of Mo2(DpyF)4 with excess HBF4 in THF. The reactions of 1 with pyridine afforded the complex trans-[Mo2(DpyF)2(py)4][BF4]2, 2. Their UV-vis and 1H-NMR spectra have been recorded and their structures have been determined. Crystal data for 1: space group Cmca, a = 38.003(3) Å, b = 12.847(2) Å, c = 22.023(2) Å, V = 10752(2) Å3, Z = 8, with final residuals R1 = 0.0504 and wR2 = 0.1454. The two Mo atoms are bridged by two HDpyF neutral ligands. The amine groups of the two HDpyF ligands lie close to and interact with the Mo atoms, giving rise to two N-H---Mo(II) agostic interactions. Crystal data for 2: space group P21/n, a = 10.920(1) Å, b = 14.162(1) Å, c = 17.012(1) Å, β = 99.378(1) □, V = 2595.8(2) Å3, Z = 2, with final residuals R1 = 0.0443, wR2 = 0.1029. Reaction of MnCl2 with HDMpyF afforded the complex MnCl2(HDMpyF)2, 3. Crystal data for 3: space group C2/c, a = 23.719(2) Å, b = 11.548(1) Å, c = 14.342(1) Å, β = 124.07(1)□, V = 3253.8(5) Å3, Z = 1, with final residuals R1 = 0.0508, wR2 = 0.1356。 The compounds M2(dppap)(M = Cr, 4; Mo, 5) were prepared by reaction of CrCl2 and Mo2(O2CCH3)4, respectively, with lithium salt of Hdppap (Hdppap = 2-(diphenylphosphinoamino)pyridine) in THF. The complex Mo2O2(dppap)4, 6, was prepared by dissolving complex 5 in THF, and layered with hexanes in air. Reaction of [Cu(CH3CN)4][PF6] with Hdppap in CH2Cl2 afforded the complex [Cu(HDppap)2][PF6], 7. These compounds have been characterized by analytical and spectroscopic data. The structures of 4, 6 and 7 have been determined by X-ray crystallography. Crystal data for 4 : space group Pī, a = 10.321(1) Å, b = 11.991(1) Å, c = 13.813(1) Å, α = 101.235(1) □, □ = 99.821(1) □, γ = 94.478(1) □, V = 1641.0(2) Å3, Z = 1, with final residuals R1 = 0.0522, wR2 = 0.1399. The Cr-Cr distance is 1.8866(9) Å which indicates a supershort quadruple bond. Crystal data for 6 : space group C2/c, a = 21.117(1) Å, b =17.617(1) Å, c = 20.435(1) Å, β = 93.595(1)□, V = 7587.4(7) Å3, Z = 4, with final residuals R1 = 0.0480, wR2 = 0.1089. Crystal data for 7 : space group C2, a = 15.653(1) Å, b = 11.883(1), c = 12.335(1) Å, □ = 121.578(6) □, V = 1954.6(3) Å3, Z = 2, with final residuals R1 = 0.0491，wR2 = 0.1413.
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Liang, Shiu-Chi y 梁修啟. "Chemistry of Rhenium and Copper Complexes Containing Polydentate Nitrogen Ligands". Thesis, 2002. http://ndltd.ncl.edu.tw/handle/86968163511334787029.
Texto completoResumen
碩士中原大學
化學研究所
90
This thesis discuss the chemistry of transition metal complexes containing polydentate ligands. The complex [tptH3][CuCl4]Cl, 1, was prepared by reaction of CuCl2·2H2O with tpt (tpt = 2,4,6-tri(2-pyridyl)-1,3,5-triazine) in HCl(aq). The spectroscopic data of 1 has been recorded and the structure of 1 determined by X-ray crystallography. Crystal data for 1: space group P21/n, a = 10.3768(12) Å, b = 14.391(2) Å, c = 14.876(2) Å, β= 97.989(11) □, V = 2200.0(5) Å3, Z = 4, R1 = 0.0741 and wR2 = 0.1429. The complex [tptH3][CuBr4]Br, 2, was prepared by reaction of CuBr2 with tpt in HBr(aq). The spectroscopic data of 2 has been recorded and the structure of 2 determined by X-ray crystallography. Crystal data for 2: space group P21/n, a = 10.3768(12) Å, b = 14.391(2) Å, c = 14.876(2) Å, β= 97.989(11) □, V = 2200.0(5) Å3, Z = 4, R1 = 0.0741 and wR2 = 0.1429. The tptH3 cations in complexes 1 and 2 were interacted with anions through intermolecular hydrogen bonds. The complex ReBr(CO)3(HDpyF), 3, was prepared by reaction of ReBr(CO)5 with HDpyF (HDpyF = N,N ′-di(2-pyridyl)formamidine) in THF. The spectroscopic data of 3 has been recorded and the structure of 3 determined by X-ray crystallography. Crystal data for 1: space group P21/c, a = 10.7610(13) Å, b = 9.065(2) Å, c = 16.189(2) Å, β= 91.523(8) □, V = 1578.7(4) Å3, Z = 4, R1 = 0.0567 and wR2 = 0.1373. The complex Re(CO)3Br(HDMepyF), 4, was prepared by reaction of ReBr(CO)5 with HDMepyF (HDMepyF = N,N ′-di(6-methyl-2-pyridyl)formamidine in THF. The spectroscopic data of 4 has been recorded and the structure of 4 determined by X-ray crystallography. Crystal data for 4: space group P ī, a = 7.044(2) Å, b = 10.170(3) Å, c = 16.189(2) Å, α= 83.07□, β= 82.54(3) □, γ= 77.35□, V = 917.8(5) Å3, Z = 2, R1 = 0.0540 and wR2 = 0.1297. The HDpyF and HDMepyF ligands in complexes 3 and 4 were coordinated to Re atoms in bidentate fashions and the Re metal centers form facial geometry with its ligands.