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1
Sze-To, Lap, i 司徒立. "The structural chemistry of coordination compounds containing d-block or f-block metals". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B45204470.
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Aucott, Stephen Mark. "Coordination chemistry of aminophosphine ligands". Thesis, Loughborough University, 1999. https://dspace.lboro.ac.uk/2134/34492.
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The reaction of [MCl2(cod)] (M = Pt, Pd) with two equivalents of 2-(diphenylphosphinoamino)pyridine, Ph2PNHpy, in warm acetonitrile led to cationic complexes of the type cis-[MCl(Ph2PNHpy-P,N){Ph2PNHpy-P}][Cl] (M = Pt, Pd) which exhibit broad single 31P{1H} NMR resonances due to their dynamic pyridyl exchange behaviour in solution. A single crystal X-ray diffraction study of the platinum species confirmed the proposed structure and revealed that adjacent complex molecules were held together by hydrogen bonding to the same chloride counter-ion. The bromo- and iodo-cis[MX(Ph2PNHpy-P,N){Ph2PNHpy-P}][X] (M = Pt, Pd; X = Br, I) complexes were obtained by metathesis from the corresponding chloride complex.
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Chotalia, Rohit. "The synthesis and coordination chemistry of novel oligopyridine ligands". Thesis, University of Cambridge, 1993. https://www.repository.cam.ac.uk/handle/1810/272580.
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Reinhardt, Maxwell James. "Metal complexes containing non-innocent ligands for functional materials". Thesis, University of Edinburgh, 2013. http://hdl.handle.net/1842/11723.
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The existence of complexes of that display non-innocence has been of interest in the field of coordination chemistry since the investigations of square-planar dithiolene complexes of the late transition metals in the 1960s. The ligands used in these systems are termed “non-innocent” when bound to a number of the late transition metals, because the orbital energy levels are similar to those of the central metal ion. This allows there to be significant electron delocalisation over the complex with the potential for the complexes to exist in a number of electronic states due to the combined electrochemical activity. In 1966, Jørgensen classified innocence as ligands that “allow oxidation states of the central atoms to be defined”, thus by this logic non-innocent ligands are defined as complexes where the precise oxidation states of the ligand and metal are ambiguously assigned. However it should be noted that no ligand is inherently non-innocent, but rather the ligand may behave in a non-innocent manner under the right circumstances. The qualification of non-innocence should therefore only be applied to combinations of metal and ligand that result in the aforementioned properties. In this thesis, the term “non-innocent” will be used to define ligands that often possess non-innocent behaviour when complexed to the metal centres they are bound to. A general form of ligand that displays non-innocent behaviour is that of the 1,2-bidentate moiety with an unsaturated carbon backbone. The chelating donor groups (X) are either O, NH, S, or a combination of the three. The central transition metal is generally a late metal that favours a square-planar geometry, because the planarity of the complex is crucial for electron delocalisation within the molecule and molecular interactions in the solid material. When the metal is nickel or platinum for example, their square-planar complexes with such ligands have shown threemembered electron-transfer series. Specific examples of ligands that have been shown to display non-innocent behaviour are those of catechol (1,2-dihydroxybenzene) and 1,2-diaminobenzene, where the unsaturated backbone is provided by a phenyl group. The electronic nature of these compounds has been extensively investigated by the groups of Pierpont and Lever, with focus on their redox and magnetic properties. The combined metal and ligand redox activity results in interesting magnetic behaviour, with potential for magnetic exchange interactions between a paramagnetic metal centre and the radical ligand or between two radical ligands mediated by a diamagnetic metal centre. This research has been advanced by Wieghardt and co-workers who have performed experimental and theoretical examination of non-innocent complexes of 1,2-substituted phenyl chelates, where the donor group is a combination of O and NH. These studies have focused on the understanding the nature of the metal-ligand interactions to apply to biological systems, such as those observed at the active site of enzymes that act upon molecules with similar moieties to the non-innocent ligands. Compounds of catechol may be referred to as dioxolenes in analogy to the sulfur-based dithiolenes. The deprotonated, dianionic form of catechol is known as catecholate (cat), which can be readily oxidised to the monoanionic o-semiquinone (SQ) and neutral o-benzoquinone (Q) forms. It has been seen that catecholate compounds can be described by localised electronic states with defined oxidation states, unlike many of the dithiolene class of molecules. However these states can exist in equilibrium with each other when the metal and ligand orbitals are close in energy, with differences in the charge and spin definition in what has been described as “valence tautomerism”. Therefore, although the complexes may not be seen as non-innocent by definition that their oxidation states are not ambiguous, it is still a useful description due to the potential for easily accessible charge states. Metal dithiolene complexes, where the metal is coordinated by one or more ligands with two S-donor atoms linked by a conjugated backbone, are one of the best researched of the non-innocent class of molecules. The square-planar bis-dithiolenes of the late transition metals have interesting magnetic, optical and electrical properties arising from the delocalised nature of the constituent metal and ligand orbitals, which has enabled their use for a wide range of applications such as non-linear optics, transistors and near-infrared switches. Of particular interest is the ability to fine tune the electrical properties to fit the application by changing the substituents on the core dithiolene moiety. For example, Anthopoulos has shown that by lowering the energy of the lowest unoccupied molecular orbital (LUMO), stable n-channel conductivity can be observed in field-effect transistors (FETs). Materials based on square-planar non-innocent complexes have been tested in FETs, and been seen to display field-effect mobilities as high as 10˗2 cm2 V˗1 s˗1 as with Ni bis(o-diiminobenzo-semiquinonate) complexes. Most of these molecules are based on conjugated, chelating ligands such as 1,2-diaminobenzene and the dithiolene class of molecules. Field-effects have also been observed in square-planar Pt complexes, where the conductivity is thought to arise from beneficial Pt-Pt bonds in addition to the π-stacking between molecules. Despite the similarity to the diaminobenzene and dithiolene counterpart, there are no reports of catechol-based materials displaying field-effect properties in the literature. Catechol compounds are well-researched in the field of biological chemistry due to the prevalence of the catechol moiety and enzymes with which it interacts in nature. However they have not been examined far beyond their simple coordination chemistry or chemical characterisation.
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McCart, Mark Kevin. "Some diphosphine chemistry of the transition metals ruthenium, palladium, platinum and nickel". Thesis, University of Liverpool, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263849.
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Moneo, Corcuera Andrea. "Bistable molecular materials: triazole-based coordination chemistry of first row transition metals". Doctoral thesis, Universitat Rovira i Virgili, 2019. http://hdl.handle.net/10803/668881.
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En la present tesi doctoral presentem el magnetisme molecular bàsic de compostos de coordinació basats en un lligant di-anionico: (L-2 = 4- (1,2,4-triazole-4-il) etanosulfonato). En particular, vam estudiar el fenomen de transició d'espín d'un trímer de ferro (II) poli-aniònic en diferents escales, des d'una escala macroscòpica ("bulk") fins a nivells moleculars, acabant amb la deposició en superfície. D'una banda, el comportament SCO "macroscòpic" es va modular canviant l'empaquetatge de vidre i la connectivitat entre els trímers amb una estratègia d'intercanvi catiònic. D'altra banda, hem trobat bi-estabilitat en sistemes altament diluïts del trímer de Fe (II), en una solució mixta sòlida i en dissolució, on les forces de cooperació entre trímers s'hi han reduït fins a nivells moleculars. Aquest resultat ens anima a estudiar la deposició i el comportament del trímer en diverses superfícies amb vista a un primer acostament cap a una aplicació real. Finalment, hem fabricat una pel·lícula nanomètrica del compost sobre sílice, amb propietats de transició d'espín intactes. A més, també vam poder impulsar el procés de miniaturització més enllà de la mida nanomètrica en créixer una subcapa ordenada del complex en una superfície d'or a través d'una deposició d'alt buit.En la presente tesis doctoral presentamos el magnetismo molecular básico de compuestos de coordinación basados en uno ligando *di-*anionico: (L-2 = 4- (1,2,4-*triazole-4-*il) *etanosulfonato). En particular, estudiamos el fenómeno de transición de espín de un trímero de hierro (II) *poli-aniónico en diferentes escalas, desde una escala macroscópica ("*bulk") hasta niveles moleculares, acabando con la deposición en superficie. Por un lado, el comportamiento *SCO "macroscópico" se moduló cambiando el empaque de vidrio y la conectividad entre los trímeros con una estrategia de intercambio catiónico. Por otro lado, hemos encontrado *bi-estabilidad en sistemas altamente diluidos del trímero de Fe (II), en una solución mixta sólida y en disolución, donde las fuerzas de cooperación entre trímeros se han reducido hasta niveles moleculares. Este resultado nos anima a estudiar la deposición y el comportamiento del trímero en varias superficies en orden a un primer acercamiento hacia una aplicación real. Finalmente, hemos fabricado una película *nanomètrica del compuesto sobre sílice, con propiedades de transición de espín intactos. Además, también pudimos impulsar el proceso de miniaturización más allá de la medida *nanomètrica al crecer una *subcapa ordenada del complejo en una superficie de oro a través de una deposición de alto vacío.
At the present doctoral thesis present the basic molecular magnetism of compounds of coordination based at one binding *di-*anionico: (*L-2 = 4- (1,2,4-*triazole-4-*il) *etanosulfonato). In particular, we studied the phenomenon of transition of spin of a trimer of iron (*II) *poli-*aniònic at distinct scales, since a macroscopic scale ("*bulk") until molecular levels, ending with the deposition at surface. On the one hand, the behaviour *SCO "macroscopic" modulated capsizing the packaging of glass and the connectivity among the trimers with a strategy of exchange *catiònic. On the other hand, we have found *bi-stability at systems highly diluted of the trimer of Faith (*II), at a solid mixed solution and at dissolution, where the forces of cooperation among trimers have reduced until molecular levels. This result warms us at studying the deposition and the behaviour of the trimer at several surfaces with a view to a first approach to a real app. Finally, we have fashioned a film *nanomètrica of the compound on silica, with properties of transition of intact spin. Besides, also we could further the process of miniaturisation further of the size *nanomètrica at growing a *subcapa ordered of the complex at a surface of gold through a deposition of tall void.
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Jafarpour, Laleh. "New ligands, design and coordination chemistry with the transition metals and lanthanides". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0009/NQ38903.pdf.
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Holmes, Nicholas J. "Synthesis and coordination of stibine and bismuthine ligands with transition metals". Thesis, University of Southampton, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.299499.
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Haque, Nadera. "Coordination Chemistry of Barbituric Acid, its Diethyl Derivative and Benzildiimine with Transition Metals". Diss., lmu, 2009. http://nbn-resolving.de/urn:nbn:de:bvb:19-115621.
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De, Jongh Leigh-Anne. "Imine-donor complexes with group 6 and group 11 transition metals : coordination and dynamics". Thesis, Stellenbosch : Stellenbosch University, 2008. http://hdl.handle.net/10019.1/2001.
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Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008.In this study the coordination of ligands with several coordination sites, 2-aminoazoles (2- amino-4-methylthiazole), 2-aminobenzothiazole, 2-aminobenzoimidazole and 2- aminothiazoline and a biguanidine (N-(2-methylphenyl)imidodicarbonimidic diamide) to soft metal centres [gold(I) (group 11), chromium(0) (group 6) and tungsten (0) (group 6)] was investigated. The aminoazoles have three coordination sites, an exocyclic amine nitrogen, an endocyclic imine nitrogen and an endocyclic thioether sulphur. The biguanidine ligand has three sites for deprotonation, one central amine and two imine nitrogens, and at least five sites available for nitrogen coordination.
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Castañeda-Perea, Luis Raúl. "Imidoyl Amidine Ligands: A Versatile Framework to Build Homo and Heterometallic Complexes". Thesis, Université d'Ottawa / University of Ottawa, 2020. http://hdl.handle.net/10393/40712.
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Ligand design in general enables the formation of coordination compounds with multiple functionalities within a single framework. To date, two of the most widely studied ligands are 2,2′:6′,2′′-terpyridine (terpy) and acetylacetone (acac), whose tridentate and bidentate coordination pockets, respectively, enables the formation of metallic complexes with various geometries. The Brusso group had been incorporating imidoyl amidine (ImAm) ligands to build different materials such as organic radicals and fluorescent materials. In particular, the ligands N-2-pyridylimidoyl-2-pyridylamidine (Py2ImAm) and N-2-pyrimidylimidoyl-2-pyrimidylamidine (Pm2ImAm) were recently synthesized and have great appeal to build metallic complexes, as they poses two coordination sites similar to those in terpy and acac. The work presented herein represents the first studies involving the coordination of Py2ImAm and Pm2ImAm as discrete ligands. Our results demonstrate the versatility of these ligand frameworks, in which discrete mononuclear complexes, homometallic and heterometallic polynuclear complexes may be realized.
Chapter one serves as a brief introduction to transition metal chemistry and has a comprehensive review of the coordination chemistry of the ImAm ligand framework. In chapter two, the selective coordination of first row transition metals into the bidentate or tridentate sites of Py2ImAm is explored. The formation of these mononuclear complexes is acid-base driven, where a weak acid induces coordination to the tridentate site and a weak base leads to coordination in the bidentate site. Coordination to both sides of Pm2ImAm with manganese or iron is explored in chapter three. The results show the formation of unusual tetranuclear complexes with the metal ions in both low spin and high spin configurations. Chapter four covers the coordination to cobalt, and the formation of polynuclear complexes with different geometries using Pm2ImAm. The magnetochemistry of these cobalt polynuclear complexes is also presented and reveal a single molecule magnet behaviour for one of the complexes. Finally, in chapter five, a one-pot synthesis of copper-manganese heterometallic complexes is presented. Overall, these imidoyl amidine ligands are able to build complexes with different geometries, different electronic configurations (i.e. low or high spin), and different metal ions. These results show a great versatility of ImAm ligands and suggest the future use of these ligands by other research groups.
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Garon, Christian N. "TANTALUM(V) AND ZIRCONIUM(IV) : Coordination Chemistry of Boronates and Carboxylates to Early Transition Metals". Thesis, Université Laval, 2011. http://www.theses.ulaval.ca/2011/28751/28751.pdf.
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Shrestha, Sweta. "Application of Transition Metal Coordination for Energy Efficient Processes: Catalysis and Separation". The Ohio State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=osu1502975499629018.
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Clough, Benjamin. "New scandium and titanium borylimido chemistry". Thesis, University of Oxford, 2017. https://ora.ox.ac.uk/objects/uuid:1a9dbfb3-98c3-4fd6-96ac-5fba09f3ffcd.
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This Thesis reports the synthesis and reactivity of scandium and titanium borylimides. New, versatile synthetic routes to such complexes of these two metals were targeted, and their reactions with small, unsaturated compounds were explored, with a particular focus being the reactivity of alkynes with these systems. Chapter One provides a background on Group 4 imido and hydrazido complexes. Group 4 alkoxyimides are also reviewed, as well as the developing field of rare earth imides. The Chapter focuses on the synthesis, structure, and stoichiometric and catalytic reactions of these complexes with unsaturated substrates, and ends with a description of the handful of known transition metal borylimides. Chapter Two first describes the synthesis and structures of new titanium borylimido synthons prepared from Ti(NMe2)2Cl2. From the borylimide Ti{NB(NAr'CH)2}Cl2(py)3 are then formed five new compounds supported by a range of tridentate, nitrogen-based ligands. Chapter Three describes the synthesis of half-sandwich titanium borylimides through tertbutylimide/borylamine exchange. A sandwich compound is also described, and the electronic structures of these complexes are analysed by DFT, QTAIM and NBO studies. Reactivity with heteroallenes, and exchange reactions with amines are also explored. Chapter Four describes the reactivity of diamide-donor-supported titanium borylimides with terminal alkynes. The principal reaction outcomes are [2+2] cycloadditions and CâH bond activations, and an interesting CâF bond activation is also described. Kinetic studies of some reactions are presented, and will be supported by further DFT studies. Chapter Five explores attempts to prepare the first rare earth borylimide. Kinetic and computational evidence is presented for the existence of a transient scandium borylimide which rapidly undergoes interesting sp, sp2 and sp3 CâH bond activations. Chapter Six presents full experimental procedures and characterising data for the new complexes reported.
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Carson, Cantwell G. "Noble and transition metal aromatic frameworks synthesis, properties, and stability /". Diss., Atlanta, Ga. : Georgia Institute of Technology, 2009. http://hdl.handle.net/1853/29657.
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Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2009.Committee Chair: Rina Tannenbaum; Committee Co-Chair: Rosario A. Gerhardt; Committee Member: E. Kent Barefield; Committee Member: Karl I. Jacob; Committee Member: Preet Singh; Committee Member: R. Bruce King. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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Kuchenbeiser, Glenn Richard. "Reactivity of bis(amino)cyclopropenylidenes (BACs) and cyclic (alkyl)(amino)carbenes (CAACs) coordination chemistry, catalysis, and small molecule activation /". Diss., [Riverside, Calif.] : University of California, Riverside, 2009. http://proquest.umi.com/pqdweb?index=0&did=1899480521&SrchMode=2&sid=4&Fmt=2&VInst=PROD&VType=PQD&RQT=309&VName=PQD&TS=1269286714&clientId=48051.
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Thesis (Ph. D.)--University of California, Riverside, 2009.Includes abstract. Available via ProQuest Digital Dissertations. Title from first page of PDF file (viewed March 10, 2010). Includes bibliographical references. Also issued in print.
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Cuevas-Chávez, Cynthia. "Synthèse, structure et réactivité de complexes de platine et d'iridium à ligands phosphinodi(benzylsilanes)". Thesis, Toulouse 3, 2019. http://www.theses.fr/2019TOU30196.
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Une chimie riche et des possibilités d'applications dans un large éventail de domaines (par exemple, l'activation de petites molécules, les transformations sélectives, y compris les développements catalytiques, etc.) des composés de type pince à base de silicium avec des métaux de transition ont été attestés par des progrès remarquables en chimie de coordination ainsi qu'en organométallique. Cela est dû aux propriétés remarquables des atomes de Si qui génèrent des centres métalliques riches en électrons labellisant de manière concomitante les substituants trans. Cependant, malgré la pléthore d'arrangements de telles espèces dans la littérature (par exemple, le cadre, le nombre et la nature des points d'ancrage), les dérivés métalliques à ligands polydentates incorporant deux atomes de silicium sont limités, de même que l'étude de leur réactivité. Par conséquent, cette thèse présente la synthèse, la structure et la réactivité de nouveaux complexes de platine et d'iridium supportés par le ligand de type pince "SiPSi". Il est intéressant de noter que le complexe PtII carré-plan de formule trans-[(SiPSi)Pt(PPh3)] (SiPSi = P(o C6H4CH2SiMe2)2Ph) réagit de manière réversible avec de petites molécules, H2 et CO, formant le dihydrure et le dicarbonyle correspondants, espèces à 18 d'électrons, respectivement. D'autre part, le complexe dimérique [Ir(SiPSi)(µ-Cl)]2 se dissocie dans une solution benzénique pour donner l'espèce monomère à 14-électrons [Ir(SiPSi)Cl] qui réagit facilement avec des donneurs à deux électrons. Les configurations à 16- et 18-électrons sont obtenues en fonction principalement de l'encombrement stérique dans le cas des dérivés P. Différentes dispositions de ligands L sur des espèces de 18-électrons (L = CNCD3, CO) et le processus d'isomérisation ont également été mis en évidence. De plus, même si l'iridium a tendance à effectuer des additions oxydatives, nous avons également montré que la liaison agostique Si-H peut favoriser l'activation par C-H d'un groupe méthylène acide adjacent menant à un ligand tétradentateThe rich chemistry and applicability in such a wide range of fields (e.g. small molecule activation, selective transformations including catalytic developments, etc.) of silicon based pincer-like compounds with transition metals has been witnessed by the remarkable advances in coordination chemistry as well as in organometallics. This is due to the outstanding properties of Si atoms which generate electron rich metal centres concomitantly labilizing trans substituents. However, despite all the plethora of arrangements of such species throughout the literature (e.g. framework, number and nature of anchoring points), metal derivatives with polydentate ligands incorporating two silicon atoms are limited as is the study of their reactivity. Therefore, this thesis presents the synthesis, structure and reactivity of novel Platinum and Iridium complexes supported by the "SiPSi" pincer-type ligand. Interestingly, the square-planar PtII complex of formula trans-[(SiPSi)Pt(PPh3)] (SiPSi = P(o-C6H4CH2SiMe2)2Ph) reversibly reacts with small molecules, H2 and CO, forming the corresponding dihydride and dicarbonyl 18-electron species, respectively. On the other hand, the dimeric complex [Ir(SiPSi)(µ-Cl)]2 dissociates in benzene solution to yield the 14-electron monomeric species [Ir(SiPSi)Cl] which readily reacts with two electron donors. 16- and 18-electron configurations are obtained depending mainly on sterics in the case of P-derivatives. Different dispositions of L ligands on 18-electron species (L = CNCD3, CO) and isomerisation processes were also evidenced. Moreover, even if iridium is prone to perform oxidative additions, we also showed that Si-H agostic bonding can favour C-H activation of an adjacent acidic methylene group leading to a tetradentate ligation
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Ruffray, Kévin. "Synthèse et étude physico-chimique de systèmes d-f hétérométalliques moléculaires et auto-assemblés". Thesis, Montpellier, Ecole nationale supérieure de chimie, 2015. http://www.theses.fr/2015ENCM0025/document.
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Les interactions qu’un métal f entretient avec son environnement sont étudiées dans de nombreux domaines (industrie nucléaire, électronique, …). Pourtant, ces phénomènes sont souvent mal compris d’un point de vue fondamental. Les interactions qui peuvent s’établir entre métaux d et métaux f ont déjà été en partie étudiées, principalement dans le domaine du magnétisme. Les phénomènes de transfert de charge ont cependant été beaucoup moins analysés, malgré une importance croissante dans de nombreux systèmes. Cette étude se propose de développer des systèmes moléculaires permettant d’étudier un certain nombre de propriétés physico-chimiques de systèmes d-4f et d-5f, ainsi que leur transposabilité vers des systèmes polymères de coordination présentant des nœuds métalliques mixtes d et f.Sur les systèmes moléculaires, les études se sont centrées sur le transfert de charge photo-induit d’un métal d vers un métal f et sur leurs propriétés électrochimiques. Pour cela il a été nécessaire de développer plusieurs systèmes de référence moléculaires à base de Ru permettant l’addition d’un métal 4f ou 5f. Les systèmes moléculaires, Ru et mixte Ru-élément f, ont été caractérisés. Des études photo-physiques et électrochimiques comparatives, expérimentales et théoriques (DFT et TD-DFT), entre les systèmes Ru simples, Ru-4f et Ru-5f, ont été menées.Les systèmes de type polymère de coordination ont été abordés afin d’étendre l’étude comparative des systèmes mixtes d-f à des composés 3D. À cette fin, la synthèse de systèmes constitués d’un métal d, d’un élément 4f et d’un ligand ditopique (2,5-dihydroxy-1,4-benzoquinone, DHBQ) a été étudiée, l’objectif étant d’intégrer de façon contrôlée un métal d au sein d’une structure polymère 4f-DHBQ déjà bien connue. Ces études ont montré que l’introduction d’un métal d dans ce type de polymère de coordination n’est pas possible dans les conditions d’études pour des raisons cinétiques. Cependant, pour ces mêmes raisons cinétiques, la présence du métal d lors de la synthèse influe de façon notable sur la morphologie des composés 4f-DHBQ ouvrant d’autres perspectives à ces systèmes 4f. Ainsi il est possible de les utiliser comme précurseurs de matériaux durs (oxydes, carbures) dont les aspects structuraux et microstructuraux sont contrôlé via les propriétés structurales et morphologiques du polymère de coordinationThe interactions between an f metal and its environment are studied in several fields (nuclear industry, electronics …). However, those phenomena are often misunderstood in a fundamental point of view. The interactions which are able to settle between d and f metals are partly studied, mainly in the field of magnetism. The charge transfer phenomena were however less studied, despite an increasing interest in numerous systems. This study intends to develop molecular systems which allow studying numerous physicochemical properties of d-4f and d-5f systems, along with their transposability towards coordination polymers systems exhibiting d and f mixed metallic nodes.On the molecular systems, studies focused on photo-induced charge transfer from a d metal to an f metal and on their electrochemical properties. In order to do this, it was necessary to develop several molecular reference systems based on Ru allowing the addition of a 4f or 5f metal. The molecular systems, Ru and mixed Ru-f element, were characterized. Comparative photo-physical and electrochemical studies, experimental and theoretical (DFT and TD-DFT), between the monometallic Ru and the Ru-4f and Ru-5f systems have been achieved.Coordination polymers systems have been broached to enlarge the comparative study of the d-f mixed systems to 3D compounds. To that end, the synthesis of systems containing a d metal, an f metal and a ditopic ligand (2,5-dihydroxy-1,4-benzoquinone, DHBQ) has been studied, the aim being the controlled integration of the d metal in a well-known 4f-DHBQ polymeric structure. These studies showed that the introduction of a d metal in this type of coordination polymers is not possible in the study conditions for kinetic reasons. However, for the same kinetic reasons, the presence of the d metal during the synthesis influences in a significant way the morphology of the 4f-DHBQ compounds, opening other perspectives to these 4f systems. Thus, it is possible to use them as hard materials precursors (oxides, carbides) whose structural and microstructural aspects are controlled via structural and morphological properties of the coordination polymer
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Clarisse, Jade. "Croissance cristalline de polymères de coordination : synthèse, suivi calorimétrique et caractérisation structurale". Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10269/document.
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Les polymères de coordination poreux appelés Metal Organic Frameworks (MOF) sont envisagés pour des développements et applications prometteuses dans la catalyse par exemple. La compréhension des mécanismes de synthèse et leurs croissances cristallines restent cependant un défi. Actuellement, seules quelques études in-situ ont été réalisées pour rationnaliser la synthèse des MOFs, comme des suivis par résonance magnétique nucléaire, par spectroscopie de masse ou par diffraction des rayons X en dispersion d'énergie. Nous proposons, l'analyse thermodifférentielle qui est une technique plus aisée à mettre en oeuvre et permet un suivi calorimétrique en continu pour identifier les phénomènes thermiques régissant la synthèse tels que la réaction de formation et la cristallisation. Grâce à ces analyses thermiques, le domaine réactionnel est déterminé et l'importance des différents paramètres influençant la synthèse sont étudiés, comme la température et les vitesses de chauffage et de refroidissement ainsi que la concentration des réactifs. Ce suivi calorimétrique a été appliqué à la synthèse de nouveaux composés de coordination poreux à base d'un dérivé tetra acide carboxylique de la porphyrine pour en comprendre les étapes réactionnelles importantes. La détermination des structures cristallines montre que certains appartiennent à la classe des Porphyrin Paddle-Wheel Frameworks. De nouvelles approches pour la synthèse de MOFs sont également proposées, en utilisant des ligands organiques acides, imines, oximes et bases de SchiffPorous coordination polymers so called Metal Organic Frameworks (MOFs) are considered for promising development and applications such as in catalyst. However, the understanding of the synthesis mechanisms and crystal growth is a challenge. Currently, only a few in-situ studies have been done to rationalize the synthesis of MOFs, such as monitoring by nuclear magnetic resonance, mass spectroscopy and energy dispersive X-ray diffraction. In this manuscript the differential scanning calorimetry is proposed as an easier technique to implement that allows a continuous calorimeter tracking to identify the phenomena which govern the synthesis such as the formation reaction and crystallization temperatures. With such thermal analyses, the temperature range of the reaction was determined and the importance of various parameters influencing the synthesis was studied, such as heating temperatures and cooling speeds or reactant concentration. This was applied to the synthesis of new porous coordination compounds based on porphyrin acid derivative in order to understand the important reaction steps. Crystal structure determinations show that some are Porphyrin Paddle-Wheel Frameworks. New approaches to the MOFs synthesis are also proposed using organic ligands like acids, imines, oximes and Schiff bases
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ORBISAGLIA, SERENA. "From pyrazole- to imidazole-based N-donor Ligands: Coordination Chemistry and Applications of New Late Transition Metals Complexes with Scorpionates, Poly(pyrazolyl)alkanes and NHCs". Doctoral thesis, Università degli Studi di Camerino, 2014. http://hdl.handle.net/11581/401839.
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The nature of ligands coordinated to the metal ion mostly determines the properties of the inorganic, organometallic or bioinorganic model compounds. The pyrazole is one of the most studied heterocyclic aromatic compounds in coordination chemistry as single ligand or incorporated in polidentate ligands, such as in poly(pyrazolyl)borates (‘scorpionates'), poly(pyrazolyl)alkanes, etc. The great versatility of the pyrazole allows the formation of several ligands with different functionalizations, which mainly influence the geometry and nuclearity of the diverse coordination complexes afforded by the reaction of the pyrazole-based chelating ligands and a metal ion. Another of the most studied heterocyclic aromatic compounds in coordination chemistry is an analogue of pyrazole with two non-adjacent nitrogen atoms, the imidazole, which represents the main structure of the most common and studied N-Heterocyclic carbenes (NHCs), in particular the imidazolâ€2â€ylidenes. These general informations arouse curiosity in main features and reactivity, synthesis and coordination modes, potential and ensured applications of various N-donor ligands, such as poly(pyrazolyl)borates or scorpionates, their isoelectronic and isosteric neutral analogues poly(pyrazolyl)alkanes and N-heterocyclic carbenes, presented, thus, in detail, in Chapter 1. The focus on the electronic and steric properties, the coordinating behaviour and several applications of scorpionates metal complexes, the state-of-art on coordination chemistry and reactivity of the poly(pyrazolyl)alkanes derivatives, the advantages of NHCs over phosphines, including ease of handling, minimal toxicity and powerful electron-donating properties, as enhanced stability of their transition metal complexes, which lead to the synthesis of highly active derivatives in homogeneous catalysis, anticipate the research work of this thesis on the nitrogen pyrazole- and imidazole-based ligands and their organometallic compounds. Beginning from Chapter 2, which describes the aims of the research work, all the chapters are divided in four sub-chapters. In the first sub-chapter differently halogen substituted bis- and tris-(pyrazolyl)borate ligands (BpBr3, TpBr3 and TpiPr,4Br) are compared in terms of electron-donor character through their interactions with various ruthenium(II) arene dimers, as also through electrochemical studies. Interestingly, an unexpected dinuclear ionic compound accounted for by its low thermodynamic stability, confirmed by theoretical calculations at the DFT level, due to steric reasons. The second sub-chapter is centered on the synthesis, characterization and crystal structure of the complexes of the second-lowest steric hindrance scorpionate ligand, TpTn, towards CuI, CuII, ZnII and CdII acceptors. A remarkable coordinative aspect of this ligand is pointed out, as well as the thermal and air stability of the relative complexes, confirmed by thermogravimetric and differential thermal analysis (TGA-DTA). By contrast, the interaction between TpTn and PtI2 proceeded through ligand decomposition, affording a monomeric complex. In the third sub-chapter, the varying, different stoichiometries and the N,N-chelating coordination modes of the bis(pyrazolyl)methanes, in particular of the two indazolyl-based regio-isomeric ligands, L1, bis(1H-indazol-1-yl)methane, and L2, bis(2H-indazol-2-yl)methane, toward XI group metal centers are studied. The synthesis and full characterization of analogous adducts of both regio-isomers allow a systematic comparison of their structural and spectral features, depending on the regio-isomeric ligand and counter-ion used, and the reaction conditions employed. The synthesis and characterization of a new series of stable, cationic gold(I/III) NHC complexes, as well as their catalytic activity in five well-established organic gold-mediated transformations, performed at the University of Strasbourg, under guidance of Director of Research Pierre Braunstein and coworkers (Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Universita'© de Strasbourg, France) is described in the fourth sub-chapter. Interestingly, various attempts to synthesize gold(III) NHC bis- or tris-pyridine complexes, as also the comparative behaviour of NHCs respect to phosphine ligands, are presented. Going further on the thesis structure, all the general procedures and experimental data are reported in Chapter 3, while the discussion and elaboration of the results are described in Chapter 4. Concluding remarks and future perspectives are discussed in Chapter 5, whereas all the references and some notes are given in Chapter 6. In Annexes section, the Curriculum Vitae, the List of Pubblications and the Contributions to Congresses are presented.
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Lake, Andrew J. "Advances in polyaromatic and ferrocenyl phosphine chemistry". Thesis, Loughborough University, 2010. https://dspace.lboro.ac.uk/2134/6329.
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Condensation of Ph2PCH2OH with a range of polyaromatic substituted secondary amines afforded a new set of 'hybrid' phosphine ligands of the type {RCH2N(CH2PPh2)CH2}2 and RCH2N(CH2PPh2)CH2CH3 (R = various planar aromatic groups). The coordination chemistry of these new mono and bidentate ligands towards a range of transition metal centres including Mo(0), Au(I), Rh(I), Ni(II), Pd(II), Pt(II) and Ru(II) was investigated. Ditertiary phosphines of the form {RCH2N(CH2PPh2)CH2}2 were found to be capable of bridging two transition metal centres in addition to forming rare examples of nine-membered cis- and trans- chelate complexes. Single crystal X-ray analysis of these coordination compounds revealed several types of inter- and intramolecular packing interactions (including a C-H···Pt interaction and slipped intermolecular π····π stacking), and also confirmed the rare trans-diphosphine coordination mode. Fluorescent emission measurements have been undertaken on these new tertiary phosphines and their coordination compounds, and these luminescent properties are discussed. A preliminary investigation into the chemosensory behaviour of selected compounds has been undertaken. Using RPCH2OH (RP = Ph2P, Cy2P or AdP = 1,3,5,7,-tetramethyl-2,4,8-trioxa-6- phosphaadamantane) as a versatile precursor, a range of ferrocenyl (Fc) tertiary phosphines have been prepared from a selection of primary and secondary amines. The coordination chemistry of these new mono and bidentate ligands towards several transition metal centres including Cr(0), Mo(0), Au(I), Rh(I), Ru(II), Pd(II) and Pt(II) was investigated. In particular, the previous chemistry was expanded to prepare several new diferrocenyl phosphines of the form {FcCH2N(CH2PR)CH2}2. In a similar manner to their polyaromatic counterparts, these ditertiary phosphines were found to be capable of coordination through both bridging and cis- / trans-chelating modes. Notably, single crystal X-ray analysis was used to confirm the formation of an extremely rare example of a dimeric trans, trans-[Rh(CO)Cl{phosphine}2]2 complex; thought to be the first crystallographically characterised metallacycle containing an Rh2Fe4 arrangement of metal centres. In addition to this {FcCH2N(CH2PR)CH2}2 chemistry, a rare example of a triferrocenyl ditertiary ii phosphine, {FcCH2N(CH2PPh2)CH2}2Fc, was prepared, as well as a macrocyclic ditertiary ferrocenyl phosphine, C10H8Fe(CH2N(CH2PPh2)CH2)2CH2. The coordination chemistry of {FcCH2N(CH2PPh2)CH2}2Fc led to the formation of two unusual examples of pentametallic diphosphine coordination complexes with a Fe3Au2 and Fe3Ru2 arrangement of metal centres. The development of a new phosphinoamine, (Ph2P)2NCH2Fc, and a new ferrocenyl iminophosphine, Ph2PCH(Ph)CH2C(H)NCH2Fc, are also discussed, in addition to a brief investigation of their coordination chemistry. Electrochemical measurements have also been undertaken on these ferrocenyl ligands and their respective coordination compounds (when purity, yield and stability would allow), and their redox chemistry discussed. A series of novel phosphorus(III) containing ligands of the forms (R)N(CH2PPh2)2 and (R)NHCOCH2N(CH2PPh2)2 (R = functionalised planar aromatic or ferrocenyl group) have been prepared. The phosphines were found to readily coordinate several transition metals including Pt(II), Pd(II) and Ru(II) to form a series of new cis- chelate and bridged bimetallic complexes. Analysis by single crystal X-ray diffraction revealed several types of inter- and intramolecular hydrogen bonding within the molecular structures of the phosphines and their coordination compounds, including the formation of several intermolecular 1D chains and the presence of an intramolecular N-H···N bond, which forces a 'scorpion-like' conformation.
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Iasco, Olga. "Aimants moléculaires à base de clusters polymétalliques : synthèse, structures cristallines et étude des propriétés magnétiques". Phd thesis, Université Claude Bernard - Lyon I, 2011. http://tel.archives-ouvertes.fr/tel-00838606.
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Les molécules-aimants, ou Single-Molecule Magnets en anglais, sont des complexes polymétalliques qui possèdent la propriété remarquable de se comporter individuellement comme des aimants. Synthétisées selon les méthodes de la chimie de coordination elles sont devenues l'objet d'une intense activité de recherche multidisciplinaire à l'interface de la chimie et de la physique. C'est dans ce contexte que se situe notre travail de thèse qui nous a conduit à synthétiser plusieurs séries de complexes polynucléaires nouveaux puis a les caractériser cristallographiquement et étudier leurs propriétés magnétiques dont les résultats sont présentés dans ce mémoire. Le premier chapitre présente l'approche théorique, expérimentale et les avancées scientifiques principales dans le domaine des molécules-aimants. Le deuxième chapitre concerne quatre séries de composés obtenus avec des ligands de type oxime. Deux de ces composés [Mn3]n et [Mn6] sont des complexes homonucléaires à base de manganèse et les deux autres [Ln2Cu2] et [Ln3Cu8] (LnIII = Dy, Gd, Tb, Y) des complexes hétéronucléaires CuII - LnIII. D'après les études magnétiques nous avons constaté que [Mn3]n, [Dy2Cu2] et [Dy3Cu8] se comportent comme des molécules-aimants mais que [Mn6] ne manifeste pas les propriétés d'une molécule-aimant. Le troisième chapitre concerne un composé tetranucléaire [Mn4] et une série de complexes dodecanucléaires [Ln4Cu8] (LnIII = Dy, Gd, Tb, Y) obtenus avec des ligands de type benzoxazoles. Les études des propriétés magnétiques ont mis en évidence le couplage antiferromagnétique des ions Mn dans le cubane [Mn4]. Pour la série [Ln4Cu8] (LnIII = Dy, Gd, Tb, Y) sur la base du complexe d'yttrium le couplage Cu-Cu a été négligé et pour le complexe [Gd4Cu8] nous avons mis en évidence des interactions Cu-Gd ferromagnétiques et Gd-Gd antiferromagnétiques. Les mesures faites sur le composé [Dy4Cu8] ont mis en évidence le comportement caractéristique d'une molécule-aimant. Le dernier chapitre présente les résultats obtenues pour un complexe tetradécanucléaire à valence mixte MnII - MnIII [Mn14] que nous avons obtenu a partir d'un ligand de type base de Schiff et dans lequel coexistent des interactions antiferromagnétiques et ferromagnétiques entre les ions manganèse avec un zero-field splitting important. La conclusion générale fait le bilan de nos résultats et donne quelques perspectives ouvertes par notre travail.
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Parrott, Suzanne J. "The coordination chemistry of hydrazide and diazenide complexes of rhenium". Thesis, University of Essex, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.315728.
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Quirk, Jeffrey. "Coordination chemistry of selenoether macrocyclic ligands with transition metal ions". Thesis, University of Southampton, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.242624.
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Hall, Christopher. "The coordination of alkanes to transition metal fragments". Thesis, University of York, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.331939.
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Hall, Andrew J. "Transition metal ion coordination in hydrophilic polymer membranes". Thesis, Aston University, 1994. http://publications.aston.ac.uk/9746/.
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The research described within this thesis is concerned with the investigation of transition metal ion complexation within hydrophilic copolymer membranes. The membranes are copolymers of 4-methyl-4'-vinyl-2,2'-bipyridine, the 2-hydroxyethyl ester of 4,4'- dicarboxy-2,2'-bipyridine & bis-(5-vinylsalicylidene)ethylenediamine with 2-hydroxyethyl methacrylate. The effect of the polymer matrix on the formation and properties of transition metal iron complexes has been studied, specifically Cr(III) & Fe(II) salts for the bipyridyl- based copolymer membranes and Co(II), Ni(II) & Cu(II) salts for the salenH2- based copolymer membranes. The concomitant effect of complex formation on the properties of the polymer matrix have also been studied, e.g. on mechanical strength. A detailed body of work into the kinetics and thermodynamics for the formation of Cu(II) complexes in the salenH2- based copolymer membranes has been performed. The rate of complex formation is found to be very slow while the value of K for the equilibrium of complex formation is found to be unexpectedly small and shows a slight anion dependence. These phenomena are explained in terms of the effects of the heterogeneous phase provided by the polymer matrix. The transport of Cr(III) ions across uncomplexed and Cr(III)-pre-complexed bipyridyl-based membranes has been studied. In both cases, no Cr(III) coordination occurs within the time-scale of an experiment. Pre-complexation of the membrane does not lead to a change in the rate of permeation of Cr(III) ions. The transport of Co(II), Ni(II) & Cu(II) ions across salenH2- based membranes shows that there is no detectable lag-time in transport of the ions, despite independent evidence that complex formation within the membranes does occur.
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Anderson, Carly Elizabeth. "Synthesis of multidentate PNE ligands and their late transition metal coordination chemistry". Thesis, Durham University, 2007. http://etheses.dur.ac.uk/2598/.
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This thesis describes the synthesis of a family of potentially tridentate PNE (E = NMe, О, S, СН(_2), NPh) ligands comprising a six-membered diheteroatomic saturated ring system bearing a pendent phosphine donor arm and studies on their coordination chemistry with a selection of late transition metals. Chapter 1 comprises an overview of the nature of the bonding of phosphine, amine, ether and thioether donors to metals and reviews the dynamic behaviour of saturated heteroatom-containing ring systems in solution. Selected examples of the coordination chemistry and catalytic applications of complexes of Pd, Pt and Rh are given. Chapter 2 details the concise synthesis of variously-substituted diphenylphosphine- bearing PNE ligands, Ph(_2)PCH(_2)CH(_2)N(CH(_2)CH(_2)) (_2)E (E = NMe, 2.4-1; E = о, 2.4-2; E = S, 2.4-3; E = СН(_2), 2.4-4; E = NPh, 2.4-5; E = NCH(_2)CH(_2)PPh(_2), 2.4-7), by reaction of diphenylvinylphosphine with a cyclic secondary amine. The synthesis of both hydrochloride and chalcogen derivatives are also reported. Attempts to synthesise a related family of PNE ligands with amino-substituents at P were unsuccessful. Similar reactions of allyldiphenylphosphine with N-methylpiperazine led to the formation of Ph(_2)PCH(_2)CH(Me)N(CH(_2)CH(_2)) (_2)NMe as a result of base-catalysed isomerisation of the allyl phosphine. The complexation of the PNE ligands with a variety of Pd(II) fragments is detailed in Chapter 3. Reaction with [PdCl(_2) (MeCN) (_2)] affords the [PdCl{k(^3)-PNE}](^+) Сl(^-) salts when E = NMe, O, S and CH(_2), although when E = NPh and NCHzCHjPPha, the expected products were not obtained. A bidentate [PdCİ2{K^-PN(NMe)}] isomer of 3.1-1 was characterised crystallographically although this was indicated not to be representative of the bulk sample, which consisted mainly of the tridentate [PdCl{Kľ^-PNE}] (^+0Cl(^-)isomer. Treatment of 3.1-l with MgSO(_4) affords the unusual [PdCl{k(^3)-PNE}](^+)1/2[Mg(SO(_4))շ.41-1շՕ] complex which was characterised crystallographically. Reaction of 2.4-1 ֊ 2.4-4 with [PdCl(Me)(cod)] and [PdMe(_2)(tmeda)] affords the [PdCl(Me){K(^2)- PN(E)}] and [PdMe(^2){K(^2)-PN(E)}](^+)Cl(_1) complexes, respectively. Chapter 4 describes the coordination chemistry of the PNE ligands with Pt(II) metal fragments. The reaction of 2.4-1 - 2.4-3 with [PtCİ2(cod)] affords the doubly ligated [PtCl{K^-PN(E)} {k'-P(NE)}]^ СГ complexes with both stoichiometric and half molar equivalents of the platinum precursor. Reaction of the PNE ligands with [р\сі{ц-С1}(РЕїз)]2 gives [PtCl(PEt3){K^-PN(E)}] complexes in all cases.The coordination of the PNE ligands with Rh(I) metal centres is detailed in Chapter 5. Reaction of 2.4-1 ― 2.4-4 with [Кіі2{ц-С1}2(00)4] affords the [RhCl(CO){PNE}] complexes in all cases, although when E = NMe and ร, dynamic interconversion between [RhCl(CO){K^-PN(E)}] and [Rh(CO){K^-PNE}]^ Сl(^-) complexes is observed by low temperature NMR spectroscopy. By contrast, no isomerisation is noted when E = О. When E = NPh and NCH2CH2PPh2, the expected products were not obtained. Abstraction of the metal-bound chloride from [RhCl(CO){PNE}] proved successful when E-= NMe and S but this reaction failed to afford the expected product when E = 0， even in MeCN solution. Full experimental data and methods of preparation for the compounds in this thesis are listed in Chapter 6 with supplementary crystallographic data available in the Appendices.
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Bajwa, Somia Ehsan. "Hybrid multidentate phosphine-alkene ligands for transition metal coordination chemistry and catalysis". Thesis, University of York, 2012. http://etheses.whiterose.ac.uk/2633/.
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The development of a new class of phosphine-alkene and thio-phosphine-alkene ligands based on a chalcone ferrocene framework, represents the primary focus of this study. The synthesis and characterisation of novel ligands, ferrochalcone 32 and thio-ferrochalcone 33, are described. The related alkene-phosphine ligands, the Lei ligand 17 and novel thio-Lei ligand 46, are further detailed. The coordination chemistry of four ligands (17, 32, 33 and 46) with various transition metals (Pt, Pd, Cu, Rh and Au) has been investigated in a comprehensive spectroscopis study. Single crystal X-ray analysis has been conducted at suitable junctures within the project. A surprising finding was that some solution-state structures were found to be different when studied in the solid state. The AuI complexes-containing the ligands have been successfully used in 1,5-enyne cycloisomerisation reactions. In addition to the coordination chemistry of the novel ligand systems, some interesting findings emerged For example, AuI complex of Lei ligand 17 and monodbaPHOS 74 undergoes an interesting solid-state [2+2] intramolecular cycloaddition transformation, giving cycloadduct, 72 and 77. An interesting finding includes the presence of impurity in commercially available Pd(OAc)2. Cyclopalladation of papaverine was carried out using pure and impure Pd(OAc)2, which resulted in the identification of novel Pd-dimer complex, 86. The result suggest that nitrite contaminants derive from impurities in Pd(OAc)2, and not from the oxidation of acetonitrile mediated by metallic Pd0, explain the formation of PdII-nitrito cyclopalladated products. Photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex 90 was also observed.
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Atkinson, Nigel Anthony. "Transition metal complexes with sulphur/nitrogen donor macrocycles and related ligands". Thesis, University of Huddersfield, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.290395.
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Custer, Paul D. "Transition Metal Coordination for the Construction of Supramolecular Molecules". University of Akron / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=akron1226957658.
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Ansari, Nasrin. "Coordination properties of aminophosphine with first row transition metal nitrosyl complexes". Thesis, University of Ottawa (Canada), 1994. http://hdl.handle.net/10393/6862.
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The synthesis of the new thermolabile ironnitrosylhydride complex FeH(NO)(CO)(dppf) is reported. (dppf = 1,1$\sp\prime$-bisdiphenyl phosphino-ferrocene). The facile decomposition of FeH(NO)(CO)(dppf) is interpreted in terms of a homolysis of the Fe-H bond and of a nitrosyl transfer reaction. The synthesis of the structurally characterized iron complex Fe(O=PPh$\sb2$(2-Py))$\sb3\sp2\sp+\cdot$2BF$\sb4\sp-$, by the reaction of Fe(NO)$\sb2$(THF)$\sb2\sp+$ with PPh$\sb2$(2-Py) is described. The proposed mechanism for the formation of Fe(O=PPh$\sb2$(2-Py))$\sb3\sp2\sp+\cdot$2BF$\sb4\sp-$ involves a combination of disproportionation and oxygen transfer reactions. This dipositive iron complex is the first example of a first row transition metal chelated by the oxide of diphenyl(2-pyridyl)phosphines. The synthesis and the reactivity of the cobaltdinitrosyl monometallic Co(NO$\sb2$(PPh$\sb2(2$-Py))$\sb2\sp+\cdot$BF$\sb4\sp-$, Co(NO)$\sb2$(Py)$\sb2\sp+\cdot$BF$\sb4\sp-$, Co(NO)$\sb2$(Py)$\sb2\sp+\cdot$BPh$\sb4\sp-$ and bimetallic Co$\sb2$(NO)$\sb3$(PPh$\sb2$(2-Py))$\sb2\sp+$ -BPh$\sb4\sp-$ complexes are reported. The single crystal X-ray diffraction study of Co(NO)$\sb2$(PPh$\sb2$(2-Py))$\sb2\sp+$BF$\sb4\sp-$ shows that the aminophosphine ligands are co-ordinated through their P-donor sites. In solution, Co(NO)$\sb2$(Py)$\sb2\sp+$BF$\sb4\sp-$ was stable whereas, Co(NO)$\sb2$(Py)$\sb2\sp+$BPh$\sb4\sp-$ decomposed rapidly. The structural study of Co(NO)$\sb2$(Py)$\sb2\sp+$BF$\sb4\sp-$ has led to the proposal of a new theoretical model in which the non-bonded repulsions between the NO and L ligands of the M(NO)(L) moieties provide the most influential factor for fixing the value of the (O)N-M-N(O) angle. The structurally characterized Co$\sb2$(NO)$\sb3$(PPh$\sb2$(2-Py))$\sb2\sp+$ -BPh$\sb4\sp-$ complex is the first example of a bimetallic containing two metal-metal bonded first row transition metals with diphenyl(2-pyridyl)phosphine as a bridging ligand. It is also the first example of a Co$\sb2$(NO)$\sb3\sp+$ bimetallic core stabilized by two diphenyl(2-pyridyl)phosphine ligands coordinated by the P and N donor sites of the ligands arranged in a head-to-head fashion.
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Sheng, Xia. "Competitive transport, extraction and coordination chemistry of a number of ligands with selected transition and post-transition metal ions". Thesis, Link to the online version, 2008. http://hdl.handle.net/10019/1488.
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Rooke, Stephanie Jane. "Transition metal coordination polymers of novel siloxanes bearing N- donor groups". Thesis, Imperial College London, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.271532.
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Cordes, David B., i n/a. "Supramolecular transition metal architectures". University of Otago. Chemistry Department, 2005. http://adt.otago.ac.nz./public/adt-NZDU20060705.144929.
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This thesis describes the investigation of the coordination and supramolecular chemistry of three different types of pyridine-containing ligand with a selection of Ag(I), Cu(I), Cu(II) and Cd(II) salts. The ligand types are flexible and four-armed, rigid and four-armed and bent with two rigid arms. All the ligands also display the ability to form additional supramolecular interactions.
Chapter one introduces supramolecular chemistry and crystal engineering and covers background on several areas of current interest in these fields. Network structures, both coordination polymers and hydrogen-bonded systems, are discussed and topological analysis as a method of describing and comparing network structures is introduced. An outline of the ligand design, choice of transition metals and anions is given.
Chapter two provides a review of flexible four-armed pyridine-containing ligands and their use in coordination chemistry. The synthesis and characterisation of three flexible four-armed ligands 1,2,4,5-tetrakis(2-pyridylmethyl-sulfanylmethyl)benzene (2tet), 1,2,4,5-tetrakis(3-pyridylmethyl-sulfanylmethyl)benzene (3tet) and 1,2,4,5-tetrakis(4-pyridylmethyl-sulfanylmethyl)benzene (4tet) are given. The synthesis and characterisation of the Ag(I), Cu(II) and Cd(II) complexes formed with these three ligands are also given. The complex of [Cd(2tet)(NO₃)₄] was structurally characterised by X-ray diffraction and was found to be a discrete species. The complexes {[Ag₂(3tet)](ClO₄)₂}n̲, {[Ag₂(3tet)](PF₆)₂}n̲, {[Ag₂(3tet)](CF₃CO₂)₂}n̲, {[Ag₂(4tet)]-(ClO₄)₂�2MeCN�2CHCl₃}n̲, {[Ag₂(4tet)](PF₆)₂�6MeCN}n̲ and {[Ag₂(4tet)](ClO₄)₂-�3H₂O}n̲ were likewise structurally characterised by X-ray diffraction. All these complexes were three-dimensional coordination polymers. A comparison of the seven structures is given at the end of the chapter.
Chapter three reviews rigid four-armed pyridine-containing ligands and their use in coordination chemistry. The preparation of the rigid four-armed ligand 2,3,4,5-tetrakis(4-pyridyl)thiophene (pyth) is given. The synthesis and characterisation of the Ag(I), Cu(I) and Cd(II) complexes formed with this ligand are also given. The complexes [Ag(pyth)](BF₄)�3MeCN�CH₂Cl₂}n̲, [Ag(pyth)](PF₆)�MeCN�CH₂Cl₂}n̲, [Ag(pyth)]-(CF₃SO₃)�2MeCN�CH₂Cl₂}n̲, [Cu(pyth)](PF₆)�MeCN�CH₂Cl₂}n̲ and [(Cu₂I₂)(pyth)]-(BF₄)�1/2CH₂Cl₂�H₂O}n̲ were structurally characterised by X-ray diffraction. The complex with CuI was a two-dimensional coordination polymer, and the other four complexes were three-dimensional coordination polymers. A comparison of the five structures is given at the end of the chapter.
Chapter four begins with a review of rigid angular bridging ligands and their use in coordination and supramolecular chemistry. The preparation of the ligand bis(4-pyridyl)amine (bpa) is given. The structural arrangement of bpa in the solid state was determined by X-ray diffraction. Complexes of Ag(I), Cu(I), Cu(II) and Cd(II) formed with this ligand were synthesised and characterised. The complexes {[Ag(bpa)(MeCN)](CF₃SO₃)}n̲, {[Ag(bpa)](PF₆)�MeCN}n̲, {[Ag(bpa)](ClO₄)-�2MeCN}n̲, {[Ag(bpa)](ClO₄)}n̲, {[Ag(bpa)](NO₃)}n̲, [(Cu₂I₂)(bpa)₂]n̲, {[Cu(bpa)₂Cl₂]-�3DMF�3/2H₂O}n̲, {[Cd(bpa)₂(NO₃)(H₂O)](NO₃)}n̲, {[Cd(bpa)₂(SO₄)(H₂O)]�3H₂O}n̲, [Cd(bpaH)₂(SO₄)₂(H₂O)₂]�2MeCN and {[Cd(bpa)(SCN)₂]�1/5iPrOH}n̲ were structurally characterised by X-ray diffraction. All complexes with Ag(I) were one-dimensional coordination polymers, with two of them helical, the other three zigzag. Both complexes with Cu(I) and (II) were two-dimensional coordination polymers. One complex with CdSO₄ was discrete, with the bpa ligands mono-protonated, but all other three other Cd(II) complexes were three-dimensional coordination polymers. Seven of these complexes showed hydrogen-bonding interactions linking them together to form supramolecular structures of higher dimensionalities. A comparison of the twelve structures is given at the end of the chapter.
Chapter five is a brief summary of the outcomes of this thesis.
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Gibson, Alexander. "Syntheses and studies on transition metal complexes involving phosphine and thioether ligands". Thesis, University of Southampton, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243147.
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Jackson, N. R. C. "The chemistry of transition metals in binary non-aqueous solvents containing carbon halides". Thesis, University of Leeds, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233995.
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Habtu, Michael M. "A study of the transport, extraction and co-ordination chemistry of a number of thiourea ligands with a series of transition and post-transition metal ions". Thesis, Stellenbosch : Stellenbosch University, 2003. http://hdl.handle.net/10019.1/97374.
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Thesis (MSc)--Stellenbosch University, 2003.ENGLISH ABSTRACT: In this study, a number of mono- and di-substituted acyl(aroyl)thioureas were investigated for potential application as specific carriers (ionophores) for the transport and extraction of Ag(l) from a mixture of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(lI) ions. The experimental arrangement for the transport experiments employed a liquid membrane set up involving a 3-phase system - 2 aqueous phases (source and receiving phase) separated by a chloroform membrane incorporating the ligand. Competitive metal ion transport experiments were conducted using the liquid membrane set up. The aqueous source and receiving phases were analyzed using Atomic Absorption Spectroscopy (AAS) and results were confirmed by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICPOES). The transport results show that the N,N-dialkyl-substituted-N'-acyl(aroyl) (HL) thioureas studied, with the exception of the N,N-di-(2-hydroxyethyl)-N'-benzoylthiourea (HL3 ) and N-piperidyl-N'-4-nitrobenzoylthiourea (HL9 ), were efficient and selective for Ag(I). HL9 was also selective for Ag(l) but not efficient. HL3 was selective for Cu(II). Under the experimental conditions employed, 13% Cu(lI) was transported by HL3 . Among the N,Ndialkyl- N'-aroylthioureas, maximum Ag(l) transport was obtained by using N,N-diethyl-N'-4- chlorobenzoylthiourea (HL5 ) and N,N-di-n-butyl-N'-benzoylthiourea (HL \ Under the experimental conditions employed, the percentages of Ag(l) transported by HL5 and HL 1 were 48% and 42% respectively. The transport selectivity and efficiency of 3,3,3' ,3'-tetraethyl-1 ,1'-isophthaloylbisthiourea (H2L12 ) and N,N-diethyl-N'-camphanoylthiourea (HL13)for Ag(l) were also studied. We were particularly interested, in comparing the Ag(l) transport and extraction efficiency of these ligands with that of the HL and H2L ligands. The experimental results reveal that, of all the ligands we investigated in this study, HL 13 was the most efficient and selective carrier for Ag(l) transport. The interesting result is that, depending on the ligand concentration used, HL 13 transported 71-81% of Ag(I). Competitive two-phase metal ion solvent extraction experiments were also performed under conditions similar to the transport studies. The results show that by varying the ligand concentration in the membrane phase, up to 100% Ag(l) can be selectively and efficiently extracted from the mixture of the seven metal ions. Finally, the N,N-di-(n)-butyl-N'-benzoylthiourea (HL1) ligand and its complex with Ag(l) were synthesized. Single crystals of the complex were grown for X-ray crystallography and the crystal and molecular structure of the complex was determined. The crystal structure showed that Ag(l) is bonded to the deprotonated ligand through the S,O atoms forming interesting cluster [Ag (L - S, 0)] 4 in the solid state. This structure is monoclinic and crystallizes in the space group P21!c with a = 17.805 (4) A, b = 21.759 (4) A, c = 36.438 (7) A, f3= 96.34(3)°, Z = 8 and a final R-factor of 5.4%.
AFRIKAANSE OPSOMMING: In hierdie proefskrif is 'n aantal mono- en di-gesubstitueerde asiel(ariel) tioureums ondersoek vir moontlike gebruik as ionofore (spesifieke draers) vir die transportasie en ekstraksie van Ag(l) vanuit 'n mengsel van Co(ll), Ni(II), Cu(II), Zn(II), Cd(II), Ag(l) en Pb(lI) ione. 'n Drie-fase selsisteem is gebruik vir die transportasie eksperimente, twee waterige fases (bron- en ontvang-fase) wat geskei is met die chloroform membraan fase wat die ligande bevat. Kompeterende metaalioon transportasie eksperimente is uitgevoer met behulp van hierdie vloeistof membraan stelsel. Die twee waterige fases is deur middel van Atoomabsorpsie Spektroskopie (AAS) ge-analiseer en resultate is bevestig met gebruik van Induktief-gekoppelde Plasma-Optiese Emissie Spektroskopie (IGP-OES). Die resultate het getoon dat elkeen van die N,N-dialkiel-gesubstitueerde-N'-asiel(ariel) (HL) tioureums, met uitsondering van N,N-di(2-hidroksie-etiel)-N'-benzieltioureum(HL 3) en Npiperidiel- N'-4-nitrobenzieltioureum(HL9 ), doeltreffend en selektief was vir Ag(l) transportasie. HL9 was selektief vir Ag(I), maar die transportasie waarde was nie hoog nie, dws. dit was nie doeltreffend nie. HL3 was selektief vir Cu(II). Met gebruik van ons eksperimentele kondisies is 13% Cu(lI) getransporteer deur HL 3. Van die N,N-dialkiel-N'- ariel tioureums, is maksimum transportasie van Ag(l) verkry met gebruik van N,N-dietiel- N'-4-chlorobenzieltioureum (HL5) en N,N-di-n-butiel-N'-benzieltioureum (HL1). Met gebruik van ons eksperimentele kondisies was die persentasie transportasie van Ag(l) deur HL5 en HL 1 48% en 42% onderskeidelik. Die selektiwiteit en doeltreffendheid van 3,3,3' ,3'-tetra-etiel-1 ,t-isoftaltelblstioureumtl+L 12) en N,N-di-etiel-N'-kamfonieltioureum (HL13) vir Ag(l) transportasie is ook onderneem. Ons was besonder ge-interesseerd om die Ag(l) transportasie en ekstraksie van hierdie ligande te vergelyk met dié van die HL en H2L tipe ligande. Die eksperimentele resultate het getoon dat van al die ligande wat bestudeer is, HL 13 die doeltreffendste en mees selektiewe ionofoor was. Van besondere, belang was dat, afhangend van die ligand konsentrasie wat gebruik is, HL13 71-81% Ag(l) getransporteer het. Kompeterende twee-fase metaalioon vloeistof-vloeistof ekstraksie eksperimente is ook uitgevoer onder toestande soortgelyk aan dié van die transportasie eksperimente. Die resultate toon dat met varierende ligand konsentrasie, tot soveel as 100% Ag(l) selektief en doeltreffend geëkstrakeer word vanuit 'n mengsel van die sewe metaal ione. N,N-di-n-butiel-N'-benzieltioureum (HL1 ) ligande en die kompleks daarvan met Ag(l) is ook gesintetiseer. Enkel-kristalle van die kompleks is verkry en X-straal kristallografiese analiese is onderneem. Die kristalstruktuur toon hoedat Ag(l) gebind is aan die gedeprotoneerde ligand deur die S en Q atome en toon ook interessante [Ag(L-S,Q)]4 groepe in die vaste toestand. Hierdie struktuur is monoklinies en kristaliseer in die ruimtegroep P21!c met a = 17.805(4) Á, b = 21.759(4)Á, c = 36.438(7)Á, P = 96.34(3t, z = 8 en 'n finale R-faktor van 5.4%.
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Cetin, Anil. "TRANSITION METAL COMPLEXES OF PORPHYRIN ANALOGS AND BORATE-BASED COORDINATION COMPLEXES". University of Akron / OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=akron1176390111.
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Ghebregziabiher, Berhe Haile. "Synthesis of chiral thiourea ligands and their transition metal complexes". Thesis, Stellenbosch : Stellenbosch University, 2003. http://hdl.handle.net/10019.1/53610.
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Thesis (MSc)--Stellenbosch University, 2003.ENGLISH ABSTRACT: Modification of chitosan with benzoylisothiocyanate was attempted, however due to solvent problem the study was left incomplete till appropriate solvent is designed. N,N-diethyl-N -camphanoylthiourea (HL8), N-piperidyl-N '-camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthiourea (HL10) and N,N-diethyl-N -adamantylcarbonyl thiourea (HL11)have been synthesised and characterised for the first time. Two of these ligands HL8 and HL11, were used to form a number of transition metal complexes, namely H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], translcis-[Zn(L 8_S,0)2], translcis-[Pt(L 8_S,0)2], Ag2[(HL8-S)(L-J.1-S,O)]2, translcis- [Ni(L11-S,O)2]and translcis-[Cu(L11_S,O)2]. The new products are fully characterised by means of MS, IR spectroscopy, NMR spectroscopy, elemental (C, H, Nand S) analysis and melting point determinations. The H30+{fae-[Co(L8-S,Obn, cis-[Ni(L8- S,O)2], trans-[Cu(L8-S,O)2] and Ag2[(HL8-S)(L-J.1-S,O)]2 are also characterised by Xray diffraction analysis. The structure of the new chiral N,N-dialkyl-N' -camphanoylthiourea ligand (HL8) has a significant effect on its coordination chemistry with transition metal ions. This ligand forms H30+ {fae-[Co(L8-S,Obn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,O)2] and Ag2[(HL8- S)(L8-J.1-S,O)]2 complexes with the Co(II), Ni(II), Cu(II) and Ag(I) metal ions respectively. The spectroscopic and X-ray diffraction results of these complexes indicate a bidentate mode of coordination of the ligand (with its Sand °donor atoms) to the Co(II), Ni(II) and Cu(II) metal ions. The reaction of this ligand with silver(I) however affords the formation of a binuclear silver(I) complex exhibiting monodentate and bidentate modes of coordination within the same complex. The exclusive formation of trans-[Cu(L8-S,0)2] is a new phenomenon for the HL type thiourea ligands with Sand °donor atoms. Up to this point a maximum of 15 % trans-isomer has been reported in ltterature." All the transition metal complexes made with HL8and HL11are air stable in both the liquid and solid states except the H30+{fae-[Co(L 8-S,Ob]} Interestingly the deep green fae- H30+{fae-[Co(L8-S,Obn complex is air sensitive and the Co(II) oxidizes to Co(III) in the complex by atmospheric O2. The oxidation of Co(II) to Co(III) in the complex is confirmed by 1Hand 13CNMR spectra as well as by UV-Visible spectra of the complex. The NMR spectra of the complexes indicated the presence of one isomer in each complex except for the NMR spectra of the platinum complex of the HL8 ligand. The presence of the minor trans-[Pt(L8-S,Q)21 isomer in combination with the major cis-[Pt(L8-S,Q)21 isomer in the platinum complex was indicated by the 1H, 13Cand 195ptNMR spectra of the complex.
AFRIKAANSE OPSOMMING: Pogings om chitosan met benzoylisothiocyanate te modifiseer is onvoltooid gelaat weens die gebrek aan'n geskikte oplosmiddel. N,N-diethyl-N -carnphanoylthiourea (HL8), N-piperidyl-N -camphanoylthiourea (HL9), N-pyrrolidyl-N -camphanoylthlourea (HL10) en N,N-diethyl-N -adamantylcarbonyl thiourea (HL11) is vir die eerste keer gesintetiseer en gekarakteriseer. Twee van die ligande, HL8 en HL11, is gebruik om verskeie oorgangsmetaalkomplekse te berei, nl. H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L8-S,0)2], trans/cis-[Zn(L8 - S,0)2], trans/cis-[Pt(L8-S,0)2], Ag2[(HLB-S)(L-jl-S,0)]2, trans/cis-[Ni(L11-S,0)2] en trans/cis-[Cu(L11_S,0)2]. Die nuwe produkte is volledig gekarakteriseer deur middel van MS, IR spektroskopie, KMR spektrometrie, elemente (C, H, N en S) analise en smeltpuntbepaling. Die komplekse H30+{fao-[Co(L8-S,0)3n, cis-[Ni(L8-S,0)2], trans- [Cu(L8-S,0)2] en Ag2[(HLB-S)(L-jl-S,0)]2 is ook deur middel van X-straaldiffraksieanalise gekarakteriseer. Die struktuur van die nuwe chirale N,N-dialkyl-N'-camphanoylthiourea ligand (HL8) het In beduidende invloed op die koordinasie van hierdie ligand met oorgangsmetaalione. Die ligand vorm H30+{fac-[Co(L8-S,Ohn, cis-[Ni(L8-S,0)2], trans-[Cu(L-S,0)2] en Ag2[(HL8-S)(L8-Il-S,0)]2 komplekse met Co(ll)-, Ni(II)-, Cu(II)- en Ag(I)-ione respektiewelik. Spektroskopiese en X-straaldiffraksie-analise van die komplekse toon dat die ligande op 'n bidentate wyse d.m.v. die S- en O-donoratome met Co(II), Ni(lI) en Cu(lI) koordineer. Die reaksie van hierdie ligand met Ag(I)-ione lei egter tot die vorming van 'n dikernige silwer(I)-kompleks waarin die ligande monodentaat (S) en bidentaat (S en 0) aan die metaal gebind is. Die vorming van uitsluitlik die trans-[Cu(L8-S,0)2] in die reaksie van HL8 met Cu(lI) is 'n besondere fenomeen in die chemie van hierdie tipe ligande; in die literatuur word melding gemaak van slegs een ander trans-kompleks met hierdie ligande, en dan wel met 'n maksimum opbrengs van 15%.29 Alle oorgangsmetaalkomplekse met HLB en HL11 is stabiel indien blootgestel aan lug, ongeag of die verbindings opgelos word of in die vastetoestand verkeer, behalwe H30+{fao-[Co(L8-S,Ohn. Die diep-groen gekleurde H30+{fao-[Co(L8-S,Ohn)3]} kompleks is lugsensitief; Co(lI) word deur lugsuurstof na Co(lIl) ge-oksideer. Die oksidasie in die kompleks kan deur middel van 1H en 13CKMR spektrometrie sowel as UV-sigbare spektrofotometrie bevestig word. Die KMR spektra van alle komplekse dui op die teenwoordigheid van slegs een isomeer in oplossing, behalwe in die geval van die platinum(lI) kompleks met HL8. Die teenwoordigheid van lae konsentrasies trans-[Pt(L8-S,0)2] isomeer tesame met veel hoër konsentrasies van die cis-[Pt(L8 -S,O)2] isomeer word deur 1H, 13Cen 195ptKMR spektroskopie aangedui.
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Ahmed, Ejaz, i Michael Ruck. "Chemistry of polynuclear transition-metal complexes in ionic liquids". Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2014. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-138716.
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Transition-metal chemistry in ionic liquids (IL) has achieved intrinsic fascination in the last few years. The use of an IL as environmental friendly solvent, offers many advantages over traditional materials synthesis methods. The change from molecular to ionic reaction media leads to new types of materials being accessible. Room-temperature IL have been found to be excellent media for stabilising transition-metal clusters in solution and to crystallise homo- and heteronuclear transition-metal complexes and clusters. Furthermore, the use of IL as solvent provides the option to replace high-temperature routes, such as crystallisation from the melt or gas-phase deposition, by convenient room- or low-temperature syntheses. Inorganic IL composed of alkali metal cations and polynuclear transition-metal cluster anions are also known. Each of these areas will be discussed briefly in this contributionDieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich
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Ahmed, Ejaz, i Michael Ruck. "Chemistry of polynuclear transition-metal complexes in ionic liquids". Royal Society of Chemistry, 2011. https://tud.qucosa.de/id/qucosa%3A27774.
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Transition-metal chemistry in ionic liquids (IL) has achieved intrinsic fascination in the last few years. The use of an IL as environmental friendly solvent, offers many advantages over traditional materials synthesis methods. The change from molecular to ionic reaction media leads to new types of materials being accessible. Room-temperature IL have been found to be excellent media for stabilising transition-metal clusters in solution and to crystallise homo- and heteronuclear transition-metal complexes and clusters. Furthermore, the use of IL as solvent provides the option to replace high-temperature routes, such as crystallisation from the melt or gas-phase deposition, by convenient room- or low-temperature syntheses. Inorganic IL composed of alkali metal cations and polynuclear transition-metal cluster anions are also known. Each of these areas will be discussed briefly in this contribution.Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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Hager, Emma. "The design and synthesis of new transition metal coordination complexes as potential anti-malarial agents". Doctoral thesis, University of Cape Town, 2011. http://hdl.handle.net/11427/10667.
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Moleko, Pulleng. "The coordination and extractive chemistry of the later 3d transition metal ions with N, N'-donor imidazole-based ligands". Thesis, Nelson Mandela Metropolitan University, 2014. http://hdl.handle.net/10948/8382.
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The application of bidentate N,N'-donor ligands, such as 2,2'-biimidazole (BIIMH2) and 2,2'-pyridylimidazole (PIMH) and (1H-benzimidazol-2yl)-N-methylmethanamine (BIMAH), in the solvent extraction of base metal ions from an acidic sulfate/sulfonate medium was investigated. PIMH and BIMAH showed selectivity for Ni(II) with the only interfering ion being Cu(II) in the pH range 1.2-1.8 but BIIMH2 lacked selectivity. The extraction patterns observed were influenced by stereochemical aspects, and this agreed well with the envisaged design of nickel(II)-specific extractants through stereochemical “tailor-making” which is proposed in this study. The extraction patterns were explained from a coordination chemistry point of view using spectroscopic analysis and single crystal X-ray analysis to diagnose the geometry of the complexes formed from the interaction of the base metal ions with the ligands. The formation of the trigonal bipyrimidal [Cu(PIM)2(H2O)](SO4) complex, with a water molecule coordinated, while nickel(II) forms a square planar bisPIMH was put forward as the reason for extraction pattern observed with this ligand. Cobalt(II) also forms a bisPIMH complex but has two water molecules coordinated in the formation of a distorted octahedral complex, and this results in less extractable species. A similar observation as for PIMH was noticed in BIMAH complexation reactions. The BIIMH2 complexes were found to be distorted octahedral, through the bis-coordination of BIIMH2 and two sulfonate ions, resulting in lack of pH-metric separation of the later 3d metal ions. The stability constants data was in agreement with what was observed in the solvent extraction and coordination chemistry studies for the three ligand systems.
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Olson, Justine Rose. "Early transition metal and actinide coordination chemistry of a bicyclic guanidinate ligand: synthesis, characterization, and luminescence". Diss., University of Iowa, 2017. https://ir.uiowa.edu/etd/5588.
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The bicyclic guanidinate 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate (hpp–) has been recognized as an excellent stabilizing ligand for low oxidation state metals for about a decade. It has been used as a dinucleating anionic ligand in the synthesis of complexes containing the ‘paddlewheel’ structure motif (which often contain metal-metal multiple bonds) and is resistant to reductive cleavage by low-valent metal centers. One drawback to the ligand is that its metal complexes often have reduced solubility. This can be problematic in isolation and characterization. One solution to this problem is alkylation of the rings. Two derivatives of hpp–, tetramethyl-hppH (hpp*H) and tetraethyl-hppH (hpp”H) have published syntheses that were irreproducible by our research group.
New and easily reproducible syntheses for hpp*H and hpp”H are presented. The syntheses of (hpp*)SiMe3 and (hpp”)SiMe3, which are liquid silanes that can be isolated and purified for better stoichiometric control when transferring hpp–, hpp*–, and hpp” – onto metal centers, are also described. Chapter 3 details the synthesis of several high-valent mononuclear tantalum and zirconium complexes containing hpp– and hpp*– using these silanes. The solid-state structures of the Ta(hpp*) compounds are compared to those of the previously reported Ta(hpp) compounds.
In the course of this research, it was discovered that the M(hpp)/M(hpp*) [M = Zr, Ta] complexes were highly fluorescent, exhibiting intense Ligand-to-Metal Charge Transfer (LMCT). A series of Zr(hpp)(bpy) [bpy = 2,2’-bipyridine] complexes containing different bpy derivatives were synthesized to explore the possibility of Ligand-to-Ligand Charge Transfer, a very rare phenomenon for zirconium, and are also detailed in chapter 3. Chapter 4 describes the spectrofluorimetry of the synthesized Ta(hpp), Ta(hpp*), Zr(hpp), and Zr(hpp)(bpy) complexes.
Since hpp*– is known to change electronics at the metal center compared to hpp–, we wanted to investigate if its effects could be examined by spectroscopy. Chapter 5 describes the synthesis of several metal-oxo hpp complexes that were characterized via the M=O IR stretch. The comparison was made between MO(hpp)2L and MO(hpp*)2L [M = W, Re]. The M=O IR stretches were verified by 18O isotopic labeling. Attempts at synthesizing TaOCl3 and TaO(hpp)2L are also detailed.
In the last chapter (chapter 6), a few U(hpp) complexes were generated during our development of non-cyclopentadienyl hpp– coordination chemistry of uranium, and are discussed. Two of the complexes characterized via X-ray crystallography are diuranium complexes with UIV-UIV distances of 3.56 Å, possibly being the first compounds with U-U bonds. The new complex U(hpp*)4 is also described.
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Fleming, Kathleen. "The Gas-Phase Ligand Exchange of Select Alkaline Earth and Transition Metal ß-diketonate Complexes". Youngstown State University / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=ysu1465062889.
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Hashiguchi, Ryota. "Studies on Polynuclear Metal Complexes and Low-Dimensional Mixed-Valence Halogen-Bridged Transition Metal Complexes Based on them". 京都大学 (Kyoto University), 2017. http://hdl.handle.net/2433/225426.
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Shi, Qi. "Synthesis, coordination chemistry and reactivity of 1H-pyridin-(2E)-ylidenes and application of their transition metal complexes". Thesis, University of York, 2010. http://etheses.whiterose.ac.uk/875/.
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This thesis describes the synthesis of 1H-pyridin-(2E)-ylidenes (PYE) ligands, their coordination chemistry with late transition metals and the application of their metal complexes in selected catalytic reactions and anticancer activity. The preparation of mono- and bidentate PYE ligands was achieved from reactions between pyridinium salts and primary amines in the presence of a base. A variety of PYE ligands including chiral and bulky examples were fully characterised by a number of techniques, including single crystal X-ray diffraction. A range of transition metal precursors were tested with PYE ligands and the resulting metal complexes including Rh(I), Pd(II), Ni(II) and Ru(II) were characterised by methods including single-crystal X-ray diffraction and NMR spectroscopy to examine metal-ligand bonding and ligand dynamics. Data comparison of the solid-state structures, NMR spectroscopy and DFT calculations with respect to neutral ligands, protonated salts and metal complexes indicates that charge redistribution occurs within the PYE heterocyclic ring to give a contribution from a pyridinium-amido-type resonance structure. Strong donor character of PYE ligands was supported by IR spectroscopy and supplemented by DFT calculations. Selective cyclopalladation, directed by various ligand structural motifs was studied and steric effects were found to be dominant. A series of cationic derivatives were prepared from coordination of small molecules, e.g. CO, NH3 and pyridine and it was found that steric hindrance from the PYE N-methyl group prevents side-on coordination of ligands such as alkenes and alkynes. Application of PYE ligands in the Suzuki-Miyaura cross-coupling and enantioselective addition of diethylzinc to aldehydes was carried out. A reasonable yield (88%) was obtained for the coupling of 4-bromotoluene with phenylboronic acid using one chelating PYE derivative. Enantioselectivities of up to 21% ee for the ethyl addition of benzaldehyde were also obtained. The biological activity of two types of Ru(II) complexes derived from alkyl and aryl linked di-PYE ligands and a cationic palladacycle 31 were tested against three cancer cell lines. Complexes 31 and 40 showed promising cytotoxicity results compared with cis-platin. Overall it has been found that PYE ligands are amongst the strongest donors and that the lack of rotation about the formally exocyclic imine bond locates the N-methyl group in the vicinity of the metal. Whilst this allows the steric environment to be controlled, there other consequences such as cyclometallation and a weakening of the M-PYE bond due to steric pressure.
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Cheaib, Khaled. "Synthesis, characterization and photochemical properties of 3d transition metal supported by aroyl-hydrazone ligands". Thesis, Strasbourg, 2013. http://www.theses.fr/2013STRAF062/document.
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Ce travail de thèse explorait certains aspects de la chimie de coordination de complexes moléculaires à bases de métaux 3d (Fe, Cu, Mn et Ni) supportés par des ligands azotés de type aroyle-hydrazone. Le travail de cette thèse était plus particulièrement centré sur le développement des nouveaux ligands et la photo chimie des complexes ferriques, afin d’élucider en particulier les mécanismes de la photo réduction qui valorise un brevet du laboratoire sur la production et le stockage d’énergie solaire via la photo réduction d’ions ferriques. Les complexes mis en jeu dans le processus ont été totalement caractérisés en solution et à l’état solide. Ce phénomène prend place en solution comme en solution gelée. La cinétique du processus photochimique a été suivie par UV-Visible comme par RPE. Cette photo réduction passe par un intermédiaire radicalaire et le solvant joue le rôle du donneur des électrons. Ce processus a été totalement étudié : l’effet du solvant, l’effet de la modification dans la sphère de coordination du complexe, l’effet de la modification de la périphérie des ligands et finalement l’effet des longueurs d’ondes. D’autres domaines sont également explorés, comme le magnétisme moléculaire ou encore la catalyse homogène (oligomérisation de l’éthylène) avec des complexes à base de Ni2+This PhD thesis explored some aspects of the coordination chemistry of molecular complexes based on 3d transition metal ions (Fe, Cu, Mn and Ni) coordinated by multidentate aroyl-hydrazone ligands. The work of this thesis was particularly focused on the development of new ligands, their coordination chemistry and the photochemistry of ferric complexes. The central objective of this work was to elucidate the mechanism of the photo reduction process, in order to valorize an already accepted laboratory patent on the production and storage of solar energy. The complexes involved in the process have been fully characterized in solution and in the solid state. This phenomenon takes place in solution as in frozen solution. The kinetics of the photochemical process was followed by UV-Visible as by RPE. This photo reduction passes through a radical intermediate and the solvent plays the role of the electron donor. This process has been fully studied: the effect of the solvent, the effect of the modification in the coordination sphere of the complex, the effect of the modification of the periphery of the ligands and finally the effect of the light and different wavelengths. Other fields are also explored, such as molecular magnetism for different mono and dinuclear iron and manganese complexes or even homogeneous catalysis (oligomerization of ethylene) with complexes based on Ni(II)
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Grachvogel, David Anthony. "The synthesis and structural characterisation of the lanthanide and transition metal coordination polymers formed with novel multinucleating ligands". Thesis, Imperial College London, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.391760.
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Nama, Devendra Babu. "Synthesis, PGSE diffusion and multidimensional NMR studies on transition metal organometallic species : applications in coordination chemistry and homogeneous catalysis /". Zürich : ETH, 2007. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=17177.
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