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Kedge, Jonathan L. "Synthesis of ferrocene nucleic acid monomers and ferrocene containing drug candidates." Thesis, University of Birmingham, 2017. http://etheses.bham.ac.uk//id/eprint/7424/.
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The first ferrocene nucleic acid (FcNA) was reported by the Tucker group in 2012. Furnished with two nucleobases and two hydroxyl groups, the tetrasubstituted metallocene assumes the position traditionally occupied by the two sugars of a dinucleotide. This thesis describes the successful synthesis of two FcNA monomers; a tetrasubstituted dithyminyl variation and a disubstituted control compound bearing no nucleobases. These monomers were oligomerised, their binding characteristics assessed by thermal melting studies, and compared to other monomers belonging to the group. Through the study of these compounds the Tucker group has demonstrated that FcNA monomers behave similarly to conventional nucleic acids, displaying selective H-bonding and π-stacking interactions within a hybrid duplex. A preliminary methodology for the production of diguaninyl FcNA monomers was also explored. As published in 2014, the corresponding disubstituted systems, in which a hydroxyl and a nucleobase are linked through a sugar-like ferrocene unit, are also being investigated as potential nucleoside analogues. Adding to the groups growing library, a number of related compounds were synthesised in which the hydroxyl linker length, the planar chirality, the substitution pattern of the ferrocene and the nucleobase were varied. The compounds were electrochemically characterised and assessed for their biological activity which revealed interesting structure-activity-relationships involving both the redox potentials and chirality. Following the example of ferroquine and ferrocifen, in which existing pharmaceuticals are modified through the incorporation of ferrocene, the synthesis and preliminary biological activity of novel ferrocenyl β-blockers, in which the metallocene replaces the napthol unit of the prototypical β-blocker propranolol, is reported herein.
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Kelly, Michael Jon. "Hybrid ferrocene-based systems." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:fd46594d-98d6-4f8a-a6ab-eb5ee74ba7f3.
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This thesis explores the capacity of sterically and electronically unsaturated boranes to bind substrates of biological and environmental interest, and transduce such binding events into a photo-physical and/or electrochemical response, hence reporting the presence of these substrates. Chapter three details the synthesis of a range of novel ferrocenyl boranes featuring either a proximal hydrogen-bond donor or a second Lewis acidic centre. These novel boranes were shown to be competent at binding both cyanide and fluoride anions, with the role played by a proximal hydrogen-bond donor or a second Lewis acidic centre in anion binding investigated by both NMR and crystallographic studies. Chapter four reports the synthesis of novel pyridinyl and related boronic esters, as well as unexpected mixed alkenyl/aryl boranes. The capacity of both types of system to bind fluoride or cyanide anions in solution was investigated by UV-Vis and NMR studies. The photo-physical responses to these anions were also probed, leading to the establishment of both switch-on and switch-off fluorescent responses. Chapter five extends the knowledge derived from selective anion receptor design and combines this with recent developments in the field of frustrated Lewis pairs (FLPs) to activate, bind and report the presence of nitrous oxide (N2O) molecule. Thus, the syntheses of novel, highly Lewis acidic ferrocenyl boranes that incorporate a high degree of steric loading around the boron centre are reported. The electrochemical and photo-physical response of an FLP system to the presence of N2O was investigated leading to the development of a novel N2O reporting system.
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Tazi, Mehdi. "Nouvelles fonctionnalisations de ferrocènes." Thesis, Rennes 1, 2019. http://www.theses.fr/2019REN1S124.
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Ce travail de thèse est majoritairement consacré au développement d’une voie d’accès originale vers des ferrocènes 1,3-disubstitués basée sur une réaction de migration d’halogène. Dans un premier temps, cette réaction a été optimisée à partir de ferrocène carboxamides. Malgré des rendements modestes, il s’agit des premiers exemples de migration d’halogène contrôlée en série ferrocène. Les réactions parasites identifiées ont permis une meilleure compréhension des facteurs à maîtriser pour le bon déroulement de la réaction. Dans un second temps, nous avons appliqué avec succès la réaction de migration d’halogène à une nouvelle famille de composés aux propriétés uniques, les fluoroferrocènes. Non seulement cette approche a permis d’obtenir des ferrocènes diversement trisubstitués, mais il a également été possible d’accéder à des ferrocènes tétrasubstitués et au premier exemple de ferrocène hétéro- pentasubstituté. Finalement, une étude électrochimique préliminaire a été réalisée sur des ferrocènes originaux. La détermination des potentiels rédox a permis une meilleure compréhension des effets de substituants sur les propriétés électroniques de ces composés et laisse entrevoir le développement d’une méthode de purification originaleThis thesis is mainly dedicated to the development of an original approach towards 1,3-disubstituted ferrocenes using the halogen ‘dance’ reaction. This reaction was first optimized on ferrocene carboxamide substrates. Although moderate yields were obtained, these are the first examples of controlled halogen ‘dance’ reaction in the ferrocene series. The noticed side-reactions allowed the key parameters for the success of the reaction to be identified. The halogen ‘dance’ reaction was next successfully developed in the fluoroferrocene series, an underexplored family of molecules with specific properties. Various trisubstituted ferrocenes were obtained and the reaction was also found able to deliver original tetrasubstituted ferrocenes and the very first example of hetero-pentasubstituted ferrocene. Finally, a preliminary electrochemical study was engaged. The determination of redox potentials of some of the original ferrocene derivatives allowed a better understanding of the substituent effects on ferrocene electronic behavior. Furthermore, it lays the ground for the development of an original purification process
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Sachsinger, Niki. "Redox-active ligands containing ferrocene." Thesis, King's College London (University of London), 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.266646.
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Sansook, Supojjanee. "Biological evaluation of ferrocene derivatives." Thesis, University of Sussex, 2017. http://sro.sussex.ac.uk/id/eprint/68599/.
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Organometallic complexes containing transition metals, such as Ru(II), Os(II), Ir(III), have been moderately and recently used in medicinal chemistry as anticancer, antimalarial, antimicrobial or diagnostic agents. Current trends have led researchers to explore and define new synthetic methods in the quest for the design of new drugs and reduce the inherit associated toxic side-effects by using metal based compounds. Ferrocene based derivatives have been subjected to study for their biological and medicinal applications. Examples include ferrocenophane polyphenol, ferrocenyl quinone methides, ferrocenyl-aminoquinoline-carboxamide and a ferrocene-substituted hydroxytamoxifen, which has been proved as a potential new breast cancer therapeutic. Ferroquine displays antimalarial activity and ferrocifen is a tamoxifen-ferrocene anticancer agent. During the course of our research, we have focused on synthesizing and studying the biological activity of novel organometallic compounds containing the corresponding ferrocene moiety. We aimed to make, at least, 3 different families of compounds, which were cannabinoid receptor (CB1/CB2 receptor agonists), histone deacetylase (HDAC) selective inhibitors and general kinase inhibitors. Firstly, a review covering the state-of-the-art in bioorganometallic chemistry will be presented. Secondly, we started with the synthesis of a small library of compounds containing the following groups: ferrocenylamine, 4-oxo-1, 4-dihydropyridine and dihydroquinoline. We used aminoferrocene as a bioisostere of the adamantylamine group where previous studies of compounds containing the latter group had showed it to effectively interact with the cannabinoid receptors, CB1 and CB2. Some of our compounds displayed good to excellent potency in the nM range against the CB1 and CB2 receptors. Thirdly, we embarked to synthesise HDAC inhibitors knowing their potential as anti-cancer drugs and trying to obtain, wherever possible, enzyme isoform selectivity. One of the well-known HDAC inhibitors is suberoylanilide hydroxamic acid (SAHA). Vorinastat, as it is also known, has received Food and Drug Administration approval for treating patients with cutaneous T-cell lymphoma. The compound developed in our group by replacing ferrocene for the phenyl ring in SAHA, called JAHA, is another example of a highly potent HDAC inhibitor. Our research led to compounds where the hydroxamic acid moiety in JAHA has been replaced by a benzamide group. This transformation has produced a significant effect in delivering a potent HDAC3 selective HDAC inhibitor. This is supported by biological studies and a molecular modelling rationalisation. Next, a series of oxindole based analogues have been synthesized by the Knoevenagel condensation reaction of: 5-(pentafluorosulfanyl)-1,3-dihydro-indol-2-one and 6-(pentafluorosulfanyl)-1,3-dihydro-indol-2-one compound with: ferrocenecarboxaldehyde and pyrrole-2-carboxaldehyde. The compounds thereby synthesised have been studied against a panel of kinases, and kinase inhibitory data will be discussed and presented. In a Future directions section, we will describe the synthesis of FAAH (fatty acid amide hydrolase) inhibitors based on an aminoferrocene backbone.
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Mirri, Giorgio. "Ferrocene-based electrochemical chiral sensors." Thesis, University of Birmingham, 2011. http://etheses.bham.ac.uk//id/eprint/3140/.
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Chiral recognition, determination of enantiomeric excess and the separation of enantiomers are challenging problems for the chemist. This work has as its aim the design and syntheses of new electrochemical chiral receptors for neutral molecules. All the receptors prepared contain a ferrocene group as electroactive reporting unit. The differences among the receptors mainly relate to the binding site and the chiral group. The first type of receptor, presented in Chapter 2, consists of chiral ferrocene containing boronic acids that have been used to electrochemically sense aromatic and aliphatic chiral and achiral diols. The electrochemical determination of the enantiomeric excess of a mixture of two enantiomers of Binol performed with one of these boronic acids represents a new advance in supramolecular chiral sensing. In Chapter 3 the synthesis of ferrocene-containing chiral macrocycles of different sizes is described. The binding site is a cavity featuring a diamidopyridine moiety, with the chirality introduced through a Binol unit. These receptors showed low interaction with achiral cyclic ureas and chiral carboxylic acids. Chapter 4 describes the study of self-assembled monolayers onto gold surfaces. The monolayers are formed by ferrocene-containing amides of lipoic (thioctic) acid and, for the first time, isolipoic acid. The studies indicate that isolipoic acid could be an attractive anchor group for SAM formation when strong control over the chirality of the monolayer is required.
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Magriñá, Lobato Ivan. "Development of electrochemical DNA sensors based on the incorporation ferrocene labelled dATP." Doctoral thesis, Universitat Rovira i Virgili, 2019. http://hdl.handle.net/10803/668964.
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Aquesta tesi doctoral està enfocada en el desenvolupament de sensors electroquímics d’ADN, que són dispositius analítics descentralitzats per detectar sequencies d’ADN. Aquest tipus de sensors tenen aplicacions en moltes arees incloent: diagnostics clínics, control de malalties, anàlisi d’aliments, ciències forenses, bioterrorisme i control ambiental. Tanmateix, el sensors electroquímics d’ADN tenen algún problemes que encara s’han de solucionar, incloent la necessitat d’amplificar la sequencia d’ADN diana, la necessitat de generar ADN de cadena simple per a una posterior hibridació amb un ADN de captura complementari i finalment el marcatge d’aquest ADN hibridat per procedir amb la detecció. Aquesta tesi està enfocada en la eliminació d’alguna t’aquestes etapes per tal de simplificar i millorar els sensors electroquímics d’ADN existents. Per eliminar l’etapa de marcatge d’ADN posterior a la hibridació hem utilitzat dATP modificat amb ferrocè durant l’etapa d’amplificació. Per tal d’eliminar l’etapa de generació de cadena simple hem utilitzat dues estratègies diferents: l’ús de “tailed primers” enlloc de primers normals, o alternativament, l’amplificació de l’ADN diana en fase sòlida. Hem comprovat que el dAEFcTP s’incorpora adecuadament en experiments d’extensió de primer i hem utilitzat el dAEFcTP conjuntament amb tailed primers per desenvolupar dos sensors electroquímics per detectar els patògens: K. armiger i B. anthracis. A més, hem estudiat l’efecte que te el ratio dAEFcTP:dATP en el rendiment de l’amplificació, el pic d’oxidació de ferrocè i el límit de detecció. També hem estudiat l’efecte de la solución electrolit en el pic d’oxidació de ferrocè. Finalment, hem explorat l’ús de dAEFcTP amb el mètode isotèrmic d’amplifició d’ADN: recombinase polymerase amplification.Esta tesis doctoral está enfocada en el desarrollo de sensores electroquímicos de ADN, que són dispositivos analíticos descentralizados para la detección de secuencias de ADN. Este tipo de sensores tienen aplicaciones en muchas areas, incluyendo: el diagnóstico clínico, el control de enfermedades, el análisis de alimentos, la ciencia forense, el bioterrorismo i el control ambiental. Aun así, los sensores electroquímicos de ADN presentan problemas que aun tienen que ser resueltos, incluyendo la necesidad de amplificar la secuencia de ADN diana, la necesidad de generar ADN de cadena simple para una posterior hibridación con un ADN de captura complementario y finalmente el marcaje de este ADN hibridado para proceder con su detección. Esta tesis está enfocada en la eliminación de alguna de estas etapas para simplificar y mejorar los sensores electroquímicos de ADN existentes. Con tal de eliminar la etapa de marcaje de AD posteriora la hibridación hemos usado dATP modificado con ferroceno (dAEFcTP) durante la etapa de amplificación. Para eliminar la etapa de generación de ADN de cadena simple hemos utilizado dos estrategias distintas: el uso de “tailed primers” en lugar de primer convencionales, o alternativamente, la amplificación del ADN diana en fase sólida. Hemos comprobado que el dAEFcTP se incorpora adecuadamente en experiments de extensión de primer i hemos utilizado el dAEFcTP conjuntamente con tailed primers para desarrollar sensores electroquímicos para detectar los patógenos: K. armiger i B. anthracis. Además, hemos estudiado el electro que tiene el ratio dAEFcTP:dATP en el rendimiento de la amplificación, el pico de oxidación de ferrocene y el límite de detección del método.Además, tambinñen hemos estudiado cual es el efecto de la solución electrolyto de sorporrte en el pico de oxidaciñon del ferroceno. Finalmente hemos explorado el uso de dAEFcTP en conjuncuión con el método isotérmico de amplificación de ADN: recombinsae polymerase amplification
This thesis is focused on the development of electrochemical DNA sensors, which are decentralized analytical devices for use at the point-of-need for the detection of DNA sequences. These sensors can find widespread application in a number of diverse areas, including clinical diagnostics, disease monitoring, food analysis, forensics, bioterrorism and environmental control. However, electrochemical DNA sensors still have a number of problems that need to be addressed, including a need for the amplification of the target sequence, the need for post-amplification generation of single stranded DNA, target hybridization with a complementary capture probe and finally further reporting steps to detect the hybridized target DNA sequence. In this thesis we focused on the elimination of some of these steps to bring electrochemical DNA sensors closer to the point-of-need. To eliminate the reporting step we used ferrocene labelled dATP (dAEFcTP) to obtain already labelled target amplicons. To eliminate the single stranded generation step we followed two different strategies, the use of tailed primers instead of regular primers, or, alternatively performing DNA amplification directly on the electrode surface. The incorporation of dAEFcTP has been demonstrated in primer extension and amplification experiments. dAEFcTP and tailed primers have been used to develop a singleplex electrochemical sensor to detect K. armiger in seawater samples, and a duplex electrochemical sensor to detect B. anthracis in real samples. The effect of the dAEFcTP:dATP ratio on DNA amplification yield, ferrocene peak intensity and limit of detection has been studied, as well as the effect of the electrolyte solution on the ferrocene peak intensity. Finally, the use of dAEFcTP in combination with isothermal recombinase polymerase amplification was explored.
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Soares, Daniel da Costa e. Silva Coelho. "Estudo estrutural de produtos da degradação de [Pd2(C2,N-(dmpa)2(μ-dppf)Cl2]." Universidade de São Paulo, 2011. http://www.teses.usp.br/teses/disponiveis/75/75132/tde-17042012-114913/.
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A cristalografia por difração de raios X (DRX) é uma ciência eminentemente interdisciplinar, cujo desenvolvimento tem possibilitado o avanço de várias outras áreas científicas. A determinação das estruturas tridimensionais de substâncias, sejam elas naturais ou sintéticas, tem sido fundamental para o estudo e compreensão das relações entre propriedades físicas, químicas e terapêuticas, e a estrutura a nível atômico. Neste trabalho serão apresentados alguns aspectos teóricos sobre complexos ferrocenos e a teoria envolvida na determinação de estruturas cristalinas e moleculares por DRX, bem como a resolução e caracterização de dois complexos ferrocenos. Os resultados obtidos foram comparados com estruturas similares encontradas no Cambridge Structural Database. Nos compostos estudados no presente trabalho, 1,1\'- bis(difenilfosfina)ferroceno e oCHCl3, o Fe apresentou-se complexado a dois anéis de ciclopentadienila, em conformação estrela, os quais estão dispostos de forma equidistante do átomo de Fe, não apresentando distorções significativas. Devido à alta toxicidade da cis-platina no tratamento de neoplasias, muitos grupos de pesquisa têm dedicado seus esforços a encontrar fármacos análogos compatíveis, sendo os derivados de paládio muito visados por terem propriedades eletrônicas e estruturais semelhantes. Sabe-se que a geometria em torno do átomo de platina, na cis-Pt, é quadrado planar, como no presente caso, o que torna o composto oCHCl3 passível de ser estudado quanto à sua possível atividade. Uma das grandes incógnitas dentro da área de farmacologia é saber exatamente quais são os produtos oriundos da degradação de um determinado fármaco e através da determinação por DRX das estruturas cristalinas e moleculares dos dois compostos estudados, concluiu-se que os mesmos são oriundos da degradação do composto [Pd2(C2, N-(dmpa) 2 (μ-dppf)Cl2], uma vez que os compostos estudados tiveram suas estruturas determinadas a partir de um tubo contendo o composto inicial. Portanto, o presente trabalho possui uma considerável importância no estudo deste fármaco o qual pode ser usado no combate ao câncer.X-ray diffraction is a highly interdisciplinary science, whose development has enabled the advancement of several other scientific areas. The determination of three-dimensional structures of substances, whether natural or synthetic, have been fundamental to the study and understanding of the relationships between physical, chemical, therapeutic and structure at the atomic level. This work will present some theoretical aspects of ferrocene complexes and the theory involved in determining of molecular and crystal structures by XRD, as well as resolution and characterization of two ferrocene complexes. The results were compared with similar structures found in the Cambridge Structural Database. At the compounds studied in the present work, 1,1\'-bis(diphenylphosphine)ferrocene e {(Dichloride)[bis (diphenylphosphine)-ferrocene]Palladium(II)}oCHCl3, the Fe complexes with two cyclopentadyenil rings, at star conformation, which are disposed equidistant from Fe atom, without significant distortions. Due to the elevated toxicity of cis-platine at neoplasms, many research groups have been dedicated efforts to found compatible analog drugs, which the palladium derivatives are the most researched, because of their electronic and structural properties. It has been known that the geometry around the Pt is square planar, as like as the present case, which makes the {(Dichloride)[bis (diphenylphosphine)-ferrocene] Palladium(II)}oCHCl3, possible to be study at his possibly activity. One of the great unknowns in the area of pharmacology is to know exactly which are the products of degradation of a certain drug and determining by XRD the crystal and molecular structures of both studied compounds, concluded that they are derived from the degradation of the compound [Pd2(C2, N-(dmpa) 2 (μ-dppf)Cl2], since such compounds has their structures determined from a tube containing the [Pd2(C2, N-(dmpa) 2 (μ-dppf)Cl2]. So, the present work has considerable importance in the study of this drug which can be used against cancer.
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Appel, Markus Andreas [Verfasser], Bernd Akademischer Betreuer] Stühn, and Michael [Akademischer Betreuer] [Vogel. "Ring Rotation in Ferrocene and Ferrocene-containing Polymers / Markus Andreas Appel. Betreuer: Bernd Stühn ; Michael Vogel." Darmstadt : Universitäts- und Landesbibliothek Darmstadt, 2015. http://nbn-resolving.de/urn:nbn:de:tuda-tuprints-42268.
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Appel, Markus Andreas Verfasser], Bernd [Akademischer Betreuer] Stühn, and Michael [Akademischer Betreuer] [Vogel. "Ring Rotation in Ferrocene and Ferrocene-containing Polymers / Markus Andreas Appel. Betreuer: Bernd Stühn ; Michael Vogel." Darmstadt : Universitäts- und Landesbibliothek Darmstadt, 2015. http://d-nb.info/1111112037/34.
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Rosol, Malgorzata. "Síntesis y estudio de nuevos derivados ciclometalados del ferroceno / Synthesis and study of new cyclometallated derivatives of ferrocene." Doctoral thesis, Universitat de Barcelona, 2007. http://hdl.handle.net/10803/2799.
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The present Doctoral Thesis focuses in two main fields: alkyne-dicobaltcarbonyl complexes (PART I) and chiral ferrocene derivatives (PART II). Therefore, the obtained results can be summarized as follow: 1. The methodology designed for the synthesis of enantiomerically pure phosphane-substituted carbonyl complexes of propargyl aldehyde was not successful. The steric hindrance at position C-4 of the oxazolidin-2-one and oxazolidin-2-thione appears to difficult the removal of the auxiliary in the corresponding N-(2-alkynoyl) dicobaltcarbonyl complexes.
2. The general catalytic behavior of octacarbonyl dicobalt in the opening of cyclic ethers, such as tetrahydrofuran, by acid chlorides, leading to 4-chlorobutyl esters, has been demonstrated.
3. A pathway to access 1'-substituted and 2-substituted beta-ferrocenyl beta-amino alcohols has been developed. In this way, the synthesis with a high level of enantiomeric purity of (S)-2-amino-2-(1'-methyl)ferrocenylethanol, (pS,R)-2-amino-2-(1-trimethylsilyl)-ferrocenyl ethanol and (pR,R)-2-amino-2-(1-methyl) ferrocenyl ethanol has been achieved via their corresponding diols.
4. A general methodology which gives easy access to mono and disubstituted (1,1'- and 1,2-) 4-ferrocenyl-1,3-oxazolines has been developed.
5. A new type of interannular cyclopalladation of ferrocene has been established. The reaction seems to be quite general for 4-ferrocenyl-1,3-oxazolines with different degrees of substitution of the ferrocene moiety, provided that the C2-oxazoline substituent bears no á-hydrogens. The reaction of 4-ferrocenyl-1,3-oxazolines with palladium acetate in benzene leads to the formation of C2-symmetric complexes with two ferrocene moieties cycloplalladated at the 1' position, connected by a central palladium and four acetate bridges. When the cyclopalladation is performed by disodium tetrachloropalladate, a similar complex, but with two chloride bridges, is obtained. The 3-palladium acetate complexes can be converted into the 2-palladium chloride ones by treatment with lithium chloride in methanol. The structures of both types of complexes have been thoroughly studied by spectroscopy and by X-ray diffraction.
6. Cyclic voltammetric studies of these novel interannular palladacycles have been performed.
7. The µ-chloro bridged dipalladium complex (S)-84 undergoes bridge-splitting with triphenylphosphine leading in nearly quantitative yield to the monomer complex (S)-95. On the other hand, the reaction of (S)-84 with iodine affords 1'-iodo-2-tert-butyl-4-ferrocenyl oxazoline (S)-100. This compound has been converted into 1'-phenyl-2-tert-butyl-4-ferrocenyloxazoline (S)-101 by Suzuki coupling with phenylboronic acid. Finally, (S)-84 leads in good yields to the 1'-diphenylphosphinyl- and 1'-diphenylphosphinothioyl ferrocenes (S)-103 and (S)-104.
8. Interannularly palladated 4-ferrocenyl-1,3-oxazolines behave as active promoters of the Heck olefination, allowing the reaction to be performed at lower temperatures than previously known CN-palladacycle pre-catalysts derived from ferrocene. In the reaction medium, the olefin partner couples with the 1'-position of the ferrocene, leading to the formation of soluble palladium(0) catalytic species. For the first time, the ligand-olefin adduct has been isolated and unequivocally characterized, and further evidence favoring the involvement of a Pd(0)/Pd(II) catalytic cycle has been obtained.
9. The new interannular cyclopalladated ferrocenes have been found to be good catalysts for the asymmetric aza-Claisen rearrangement. Thus, the rearrangement of (E)-cinnamyl N-aryl benzimidates 129-131 takes place with moderate yields (40-49%) and with excellent enantioselectivity (up to 90% ee of the rearranged amide 138). Interestingly enough, the acetate-bridged 3Pd complexes lead to the (S) enantiomer of the rearranged allylic amide, while the chloride bridged 2Pd complexes (from the same (S)-enantiomer of the chiral 4-ferrocenyl-1,3-oxazoline) lead to the opposite (R) enantiomer of the amide.
10. New and outstanding catalysts for the aza-Claisen rearrangement of (E)- and (Z)-allylic trichloroacetimidates have been found. The rearrangement of both (E)- and (Z)-hexenyl trichloroacetimidates, performed in chloroform solution at 38oC with a molar 5% of the chloride bridged 1'-cyclopalladated complex, takes place with quantitative conversion and with outstanding enantioselectivity (>98% ee), according to 1H-NMR and HPLC analyses. Intriguingly, both diastereomers of the starting imidate lead to the same enantiomer (S) of the rearranged amide 142.
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Velioglu, Ozlem. "Synthesis Of Ferrocenyl Substituted Quinolines." Master's thesis, METU, 2008. http://etd.lib.metu.edu.tr/upload/3/12609785/index.pdf.
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Quinolines have been studied for over a century as an important class of heterocyclic compounds and continue to attract considerable interest due to the broad range of biological activities they possess. The incorporation of the essential
structural features of quinolines with a ferrocene moiety could provide new derivatives with unexpected and/or enhanced biological activities since several ferrocene derivatives have already been shown to be active against a number of
tumors. For this reason, we investigated the synthesis of ferrocenyl-substituted quinolines, such as 2-ferrocenylquinoline, by employing the molecular iodine catalyzed reaction between enolizable aldehydes and ferrocenyl imines, which were prepared by the condensation reactions of ferrocenecarboxaldehyde with aniline derivatives. As anticipated, these reactions produced 2-ferrocenylquinoline derivatives. By employing this ethodology, we synthesized 2-ferrocenylquinoline, 6-chloro-2-ferrocenylquinoline, 6-bromo-2-ferrocenyl-quinoline, 2-ferrocenyl-7-methylquinoline and 2-ferrocenyl-3,7-dimethylquinoline. Due to the ready availability of ferrocenylimines and aldehydes, this practical onepot
method represents a versatile synthesis of ferrocenyl-substituted quinolines.
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Onyancha, Douglas Okerio. "Synthesis, characterization and reactions of novel ferrocenylimidazoles as donor ligands." Thesis, Nelson Mandela Metropolitan University, 2010. http://hdl.handle.net/10948/1150.
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In this project a series of ferrocenylimidazole derivatives were successfully prepared and characterized using an array of analytical techniques. Reactions of ferrocenylcarbinols with N,N′-thiocarbonyldiimidazole under both solvent-free conditions and in dichloromethane are described. The reaction of ferrocenylmethanol afforded S,S-bis(ferrocenylmethyl)dithiocarbonate, the reaction of α-substituted ferrocenylcarbinols provided ferrocenylalkylimidazolides, while ω-ferrocenylcarbinols yielded ferrocenylimidazolecarbothioates. The reactions were carried out under solvent-free conditions, consistent with the principles of Green Chemistry. Ferrocenyl benzyl ethers were successfully prepared by reacting 4-ferrocenylbenzyl-1Hcarboxylate with a series of primary alcohols under catalytic condition and under a catalyst– free environment. Refluxing a mixture of alcohol-water and 4-ferrocenylbenzyl-1Hcarboxylate provided the corresponding ethers in modest yields. The same ethers were obtained at room temperature by employing potassium tetrachloroplatinate or hydrochloric acid as catalyst. Ferrocenyl-1H-imidazole, 4-ferrocenylphenyl-1H-imidazole and their corresponding ferrocenyl-3-subsitituted imidazolium salts have been successfully synthesized. The compounds were characterized and the electrochemical properties of selected imidazolium salts were examined by cyclic voltammetry. Additionally, X-ray structures of two of the imidazolium salts were determined. The imidazolium salts were found to be good catalysts for the Heck and Suzuki cross-coupling reactions.
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Cho, Yongjin. "Chiral ferrocene ligands for asymmetric cross coupling." Thesis, Imperial College London, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.300034.
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Humphries, Kristina. "Synthesis and reactivity of chiral ferrocene complexes." Thesis, Keele University, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.265643.
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Broomsgrove, Alexander Edward John. "Ferrocene based Lewis acids for anion sensing." Thesis, University of Oxford, 2010. http://ora.ox.ac.uk/objects/uuid:bfab3690-f1de-4c8d-b111-ce9083710b16.
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The synthesis, characterisation and anion binding properties of a series of mono- and bifunctional Lewis acidic borylferrocene compounds are described within this thesis. The original parent compound FcBMes₂ (3.1), revealed a versatile route for the synthesis of such borylferrocenes and subsequently the analogous compound Fc*BMes₂ (3.2) was synthesised. The anion binding properties of (3.1) and (3.2) were investigated and both were shown to bind one equivalent of cyanide. The binding event was signalled by an electrochemical shift (ca. -560 mV) and a quenching of bands at 510 or 542 nm respectively in the UV/Vis spectrum, while the mode of anion binding in the solid state was established by X-ray crystallography for [nBu₄N]⁺[(3.1)·CN]⁻. Incorporation of a suitable redox active dye (i.e. tetrazolium violet for 3.2) allowed conversion of the electrochemical response to a colorimetric change on cyanide binding. However, a competing response for fluoride is also seen for (3.1) and (3.2). Thus a two component system is reported involving (3.2) and the boronic ester FcB(OR)₂ (3.4), [where (OR)₂ = OCH(Ph)CH(Ph)O], which from previous research is known to selectively bind fluoride, and allows for selective colorimetric cyanide sensing by simple Boolean AND/NOT logic. 1,4-C₆H₄(BMes₂)[B(OR)₂] (3.5), 4,4-C12H₈(BMes₂)[B(OR)₂] (3.6) and 1,1′-fc(BMes2)(B(OR)2) (3.7) were synthesised as possible single molecules for discrimination between cyanide and fluoride. (3.5) and (3.6) proved only capable of binding one equivalent of either anion, (3.7) showed some ability to bind two equivalents of fluoride however based on ESI-MS studies although only in the presence of a large excess of anion. Systematic variation of the para-boryl substituent was investigated by synthesis of compounds FcB(XylF)₂ (4.1), FcB(Xyl)₂ (4.2) and FcB(XylOMe)₂ (4.3). Anion binding studies reveal a linear increase in fluoride binding affinity consistent with that expected based on the para,/em>-Hammett parameters, however with only minor differences, while no pattern is observed with respect to their cyanide binding capabilities. The addition of neutral and cationic peripheral substituents has been investigated through synthesis of [1,2-fc(CH₂NMe₂)BMes₂] (4.6) and [1,2-fc(CH₂NMe₃)BMes₂]⁺ (4.7). Subsequent binding studies revealed (4.6) to be moisture sensitive, however reaction of (4.7) with fluoride and cyanide led to formation of the adducts [(4.7)·F]⁻ and [(4.7)·CN]⁻. The anion affinity of (4.7) exhibits a substantial increase when compared to the parent compound (3.1). Even when compared to the isomeric 1,1′ system an increase of approximately three orders of magnitude is seen attributed to the closer nature of the cationic charge and in the fluoride adduct the presence of a cooperative intramolecular hydrogen bond. The 1,1′-bifunctional analogues of the mono-substituted systems were synthesised [e.g. 1,2-fc(BMes₂)₂ (5.1)] and shown to complex two equivalents of fluoride or cyanide in acetonitrile. The 1:1 cyanide adduct of (5.1) was isolated in chloroform however, no evidence for chelation was observed. The analogous systems 1,2-fc(BMes₂)₂ (5.5), 1,2-fc(BXyl₂)2 (5.7), and 1,2-fc(BMes₂)(BXyl₂) (5.8) were also investigated. Reaction of (5.5) with fluoride and cyanide revealed it to bind only one equivalent of either anion, neither however was bound in a chelating fashion although X-ray crystallography revealed cyanide binds exo whilst fluoride binds endo to the B···B cavity. Finally the kinetics of fluoride binding were studied by UV/Vis spectroscopy and showed a systematic increase in rate constant upon reduction of steric bulk.
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Malone, Johnathan Scott. "Magnetic Characterization of Ferrocene Derived Carbon Nanotubes." OpenSIUC, 2014. https://opensiuc.lib.siu.edu/theses/1582.
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Carbon nanotubes (CNTs) functionalized/embedded with ferromagnetic particles have several important advantages as materials for magnetic applications. The presence of ferromagnetic particles in a carbon matrix can substantially change the magnetic properties of CNT-based composites. For example, iron filled CNTs have been used as probes in magnetic force microscopy (MFM), and have potential in magnetic data storage applications. In addition, encapsulation in nanotubes provides iron nanoparticles with resistance to oxidation and mechanical damage. Chemical vapor deposition (CVD) is one of the most common single-step processes for the fabrication of high quality carbon nanotubes containing varying amounts of embedded ferromagnetic particles. This process results in the effective magnetic functionalization of CNTs and opens the door to numerous new applications. However, in order to optimize these materials for any application, their properties need to be understood. This study explores the ferromagnetic properties of carbon nanotubes containing nano-scaled iron particles which were derived from thermal decomposition of ferrocene. Both room temperature as well as low-temperature magnetic measurements will be presented and the results analyzed in the light of available theory.
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Andrade, Gustavo Fernandes Souza. "Caracterização espectroscópica da tiossemicarbazona do formilferroceno (TFF) através das técnicas SERS (Surface-Enhanced Raman Scattering) e Raman ressonante." Universidade de São Paulo, 2003. http://www.teses.usp.br/teses/disponiveis/46/46132/tde-13092006-164920/.
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Nesta dissertação o processo de adsorção da tiossemicarbazona do formilferroceno (TFF) em eletrodos de prata e ouro, em soluções aquosas 0,1 mol.L-1 de KCl e de acetonitrila. 0,1 mol.L-1 de NaClO4, foi caracterizado através da técnica espectroscópica SERS. Verificou-se através das variações espectrais que a adsorção da TFF ocorre através dos átomos N1 do grupo imínico e do S do grupo tiocarbonílico. Os processos faradáicos do TFF foram monitorados pela técnica SERS e de absorção no UV-visível. Os espectros SERS para potencial de -1,4 V (Ag/AgCl) sugerem a formação de um novo composto, produto de redução da TFF, o aminometilferroceno. Através da técnica de absorção no UV-visível verificou-se, neste potencial, o aparecimento no espectro de absorção de uma nova banda em 240 nm, atribuída à formação de tiouréia. A identificação deste dois produtos de redução indica que, para o composto TFF, o mecanismo geral de redução dos derivados de tiossemicarbazonas é obedecido. Nenhuma variação espectral, tanto utilizando a técnica SERS como a absorção no UV-visível, foi detectada durante o processo redox FeII/FeIII (E1/2=0,55 V). Os comportamentos de adsorção e faradáico da tiossemicarbazida (TSC), em eletrodo de prata em soluções aquosas neutra e ácida, foram estudados através da técnica SERS. Verificou-se que em meios neutro e ácido, a TSC está adsorvida na configuração cis para potenciais próximos de 0,0 V, interagindo com a superfície através do átomo de S do grupo tiocarbonílico e dos átomos de H ligados ao N1 hidrazínico, através da formação de pares iônicos com os ânions Cl- adsorvidos. Para potenciais mais negativos, os íons cloreto deixam a superfície e a TSC sofre reorientação, assumindo a conformação trans. Não foi observado através da técnica SERS nenhum processo faradáico em solução ácida para potenciais negativos, como havia sido proposto na literatura. A não redução do composto foi confirmada através da técnica de eletroforese capilar. Foi estudado o comportamento Raman ressonante da TFF, verificando-se a ocorrência de um mínimo no perfil de excitação experimental devido à interferência destrutiva das transições dos grupos tiossemicarbazona e ferrocenil. Os perfis de excitação teóricos foram calculados utilizando o método da transformada e os resultados dos ajustes obtidos indicam que existe considerável distorção dos modos do grupo ferrocenil na transição eletrônica em 312 nm, atribuída a n-p* do grupo tiossemicarbazona, caracterizando uma grande interação eletrônica entre os cromóforos da TFF. Para comparar o comportamento Raman ressonante do TFF com o do ferroceno, os espectros Raman ressonante deste composto foram obtidos. Verificou-se que o ferroceno apresenta, também, o efeito Raman anti-ressonante, mas as bandas vibracionais do ferroceno apresentam perfis distintos dos apresentados no composto TFF, indicando que a incorporação do grupo tiossemicarbazona no anel ciclopentadienil modifica a estrutura eletrônica do grupo ferrocenil.In this dissertation, the adsorption process of the formylpyridine thiosemicarbazone (TFF) at silver and gold surfaces in aqueous and in acetonitrile solutions has been characterized by using the SERS (Surface-enhanced Raman Scattering) technique. It has been verified that TFF adsorbs through N1 and S atoms on the metallic surfaces. The faradaic processes of TFF have been monitored through the SERS and UV-visible absorption spectroscopies. The SERS spectra at -1,4 V (Ag/AgCl) suggest aminomethylferrocene as one of the reduction products of TFF. By using the UV-visible absorption technique, it has been verified, at this potential, a new band at 240 nm in the spectrum, which indicates the presence of thiourea. The observation of these two reduction products has confirmed that the general reduction mechanism for thiosemicarbazonas works for TFF. Neither SERS nor UV-vis spectral changes have been observed during the redox process of FeII/FeIII (E1/2= 0,55 V). The adsorption and faradaic processes of thisemicarbazide (TSC) at silver electrode have also been studied by SERS technique. It has been verified that, in acidic and neutral media, the TSC is adsorbed through a cis-configuration at a potential close to 0,0 V, showing an interaction of the S atom through bond formation with the surface and through the H atoms bonded to N1 via ion pair formation with the adsorbed Cl- anions. At more negative potentials, the chloride anions leave the electrode surface and the TSC changes to trans-configuration. No faradaic process has been observed as reported in the literature. This result has been confirmed by using the capillary electrophoresis technique. The resonance Raman effect of the TFF has been studied, and the excitation profiles of the bands have been shown as minimum, which indicates an electronic interaction between the two cromophores of the TFF (thiosemicarbazone and ferrocenyl). The theoretic excitation profiles have been calculated by using the transform method, and the results of the obtained adjustment has indicated that there has been a distortion of the ferrocenyl vibrational modes for an electronic transition at 312 nm, assigned to the n-p* of thiosemicarbazone moiety. This result has indicated a great interaction between the two cromophores of TFF. In order to compare the resonance Raman behavior of the TFF with that of the ferrocene, the resonance Raman spectra of the ferrocene have been obtained. It has been verified that the two compounds present an anti-resonant Raman effect, even though the bands have presented very different excitation profiles from those observed in the TFF, which indicates that the incorporation of the thiosemicarbazone group into the ciclopentadienyl has changed the electronic structure of the ferrocenyl group.
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Fern, Glen Matthew. "Ferrocenes of Substituted Indenyl Ligands." Thesis, University of Canterbury. Chemistry, 2005. http://hdl.handle.net/10092/1266.
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This thesis describes the preparation and characterization of a variety of methyl-, trimethylsilyl-, and diphenylphosphino-substituted indenes. The indenes were then used in the preparation of bis(indenyl)iron(II) complexes. The bis(indenyl)iron(II) complexes were characterized by ¹H, ¹³C, and ³¹P-NMR, UV/visible spectroscopy, cyclic voltammetry, and mass spectrometry. The cyclic voltammetry shows an approximately linear relationship between the oxidation potential and the type of substituent and its ring position, but with increasing substitution leads to lower than expected oxidation potentials. The UV/visible spectra show two absorption bands in the visible region. The position of the bands are essentially unaffected by methyl-substitution, but the low energy band red-shifts with trimethylsilyl- and diphenylphosphino-substitution. Di(2-methylindenyl)iron(II), bis(4,7-dimethyl-indenyl)iron(II), bis(1,3-bis(trimethylsilyl)indenyl)iron(II), rac-bis(1-diphenyl-phosphinoindenyl)iron(II), rac-bis(1-diphenylphosphino-3-methylindenyl)iron(II), and rac-bis(1-diphenylphosphino-2,3-dimethylindenyl)iron(II) were characterized by X-ray crystallography.The planar chiral ferrocenylphosphine bis(1-diphenylphosphinoindenyl)iron(II) is observed to undergo a facile ring-flipping isomerization from the meso isomer to the racemic isomer in THF at ambient temperature. The isomerization is slowed by the addition of the noncoordinating solvent chloroform, but is accelerated by the addition of LiCl. Rate and activation parameters for the isomerization have been determined to be: kobs = 1.6 x 10⁻⁵ s⁻¹ at 23 ℃, ΔH‡ = 58 ± 4 kJ mol⁻¹, ΔS‡ = −140 ± 15 J mol⁻¹ K⁻¹. Deuterium labeling of bis(1-diphenylphosphinoindenyl)iron(II) in the 3- and 3ʹ-position ruled out the isomerization proceeding by [1,5]-proton shifts or dissociative mechanisms. The proposed mechanism for the isomerization proceeds via coordination of two THF ligands with ring-slippage of one of the indenyl ligands until it is coordinated through the phosphine. Coordination of the indenyl ligand by the other face leads to the formation of the other isomer.The heterobimetallic complexes (bis(1-diphenylphosphinoindenyl)iron(II))-cis-dichloropalladium(II), (bis(1-diphenylphosphinoindenyl)iron(II))-cis-dichloro-platinum(II), and [(cyclooctadiene)(rac-bis(1-diphenylphosphinoindenyl)iron(II))-rhodium(I)] tetraphenylborate were prepared. Attempts to prepare dichloro(bis(1-diphenylphosphinoindenyl)iron(II))nickel(II) lead to the formation of trans-dichloro(bis(1-diphenylphosphinoindene))nickel(II). The complex (bis(1-diphenyl-phosphinoindenyl)iron(II))-cis-dichloropalladium(II) is able to catalyze the cross-coupling of bromobenzene with n-/sec-butylmagnesium chloride. However. the reaction is not selective with isomerization of the alkyl group and reduction of the halide occurring via a β-hydride elimination mechanism.
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Kelly, Glenn Anthony. "Synthetic studies of ferrocene-containing monomers and polymers." Thesis, Bangor University, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.273670.
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Maharjan, Bidhya L. "FERROCENE-FUSED DERIVATIVES OF ACENES, TROPONES AND THIEPINS." UKnowledge, 2015. http://uknowledge.uky.edu/chemistry_etds/53.
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This research project is concentrated on tuning the properties of small organic molecules, namely polyacenes, tropones and thiepins, by incorporating redox-active transition metal centers π-bonded to terminal cyclopentadienyl ligands. Organometallic-fused acenequinones, tropones, thiepins and cyclopentadiene-capped polyacenes were synthesized and characterized. This work was divided into three parts: first, the synthesis of ferrocene-fused acenequinones, cyclopentadiene-capped acenequinones and their subsequent aromatization to polyacenes; second, the synthesis of ferrocene-fused tropones, thiotropones and tropone oxime; and third, the synthesis of ferrocene-fused thiepins. Ferrocene-fused quinones are the precursors to our target complexes. Our synthetic route to ferrocenequinones involved two-fold aldol condensation between 1,2-diformylferrocene and naphthalene-1,4-diol or anthracene-1,4-diol, and four-fold condensation between 1,2-diformylferrocene and 1,4-cyclohexanedione. Reduction of ferrocene-fused quinones with borane in THF resulted in ferrocene-fused dihydroacenes. Attempts to reduce ferrocene-fused acenequinones with sodium dithionite led to metal-free cyclopentadiene- (Cp-) capped acenequinones. Cp-capped acenequinones were aromatized to bis(triisopropylsilyl)ethynyl polyacenes by using lithium (triisopropylsilyl)acetylide (TIPSC≡CLi) with subsequent dehydroxylation by stannous chloride. The compounds were characterized by using spectroscopic methods and X-ray crystallography. Further, the electronic properties of these compounds were studied by using cyclic voltammetry and UV-visible spectroscopy. Cyclic voltammetry showed oxidation potentials of Cp-capped TIPS-tetracene and bis-Cp-capped TIPS-anthracene as 0.49 V and 0.61 V, respectively (vs. ferrocene/ferrocenium). The electrochemical band gaps were 2.15 eV and 2.58 eV, respectively. Organic thin-film transistor device performance of Cp-capped polyacenes was studied using solution deposition bottom-contact, bottom-gate (BCBG) device architecture and the resulting performance parameters are described herein.
Similarly, we are also interested in potential applications of metallocene-fused tropones and derivatives as organic electronic materials. Condensation of 1,2-diformylferrocene with acetone or 1,3-diphenylacetone in the presence of KOH resulted in the ferrocene-fused tropone (η5-2,4-cyclopentadien-1-yl)[(1,2,3,3a,8a-η)-1,6-dihydro-6-oxo-1-azulenyl]iron (1, R = H, E = O) and its 5,7-diphenyl derivative (1, R = Ph, E = O) as previously reported by Tirouflet. The use of piperidine as base resulted in Michael addition of piperidine to one of the carbon-carbon double bonds of the tropones. Lawesson’s reagent converted the ferrocene-fused tropones to either a thiotropone (1, R = H, E = S) or a detached 5,7-diphenylazulenethiol (2). Reaction of the ferrocene-fused thiotropone with hydroxylamine gave the corresponding oxime (1, R = H, E = NOH). Products were characterized by using spectroscopic methods and X-ray crystallography. Their electronic properties were studied by using cyclic voltammetry and UV-visible spectroscopy.
The third project involved the two-fold aldol condensation of 1,2-diformylferrocene with dimethylthioglycolate S-oxide in the presence of freshly distilled triethylamine, which gave mono- and di-dehydrated products. Deoxygenation of the ferrocene-fused thiepin S-oxide with 2-chloro-1,3,2-benzodioxaphosphole in the presence of pyridine resulted in the corresponding thiepin. The ester groups of the thiepin and thiepin S-oxide were hydrolyzed under basic conditions to give carboxylic acids, which were converted into acid chlorides using oxalyl chloride. Attempts to decarboxylate the thiepin and thiepin S-oxide diacids resulted in decomposition.
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Hoffmann, Viktor [Verfasser]. "Ferrocene as Functional Subunits in Macrocycles / Viktor Hoffmann." München : Verlag Dr. Hut, 2017. http://d-nb.info/1139538497/34.
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Winder, Robert John. "The synthesis of some ferrocene substituted porphyrinic macrocycles." Thesis, University of Nottingham, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.315068.
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Roberts, Holly Victoria. "Ferrocene conjugated DNA for biosensing and antisense applications." Thesis, University of Birmingham, 2018. http://etheses.bham.ac.uk//id/eprint/8663/.
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In order to enhance the sensing capabilities of DNA, an array of tags and modified nucleic acids have been synthesised. This thesis studies both the sensing capabilities and the stability of electrochemical DNA reporters based on the redox active molecule ferrocene. The topics covered are as follows: 1. Two synthetic ferrocene nucleic acid (FcNA) DNA mimics and a redox-active tag based on two covalently connected ferrocene molecules were incorporated into the backbone of a DNA strand in a central position and the 5’ end of a DNA strand, respectively. These probes were then used to form mixed monolayers and their stability was assessed. DNA target detection was possible with square wave voltammetry due to the unusual reliance of this technique on the ‘critical frequency’ of the redox active molecule. 2. DNA probes containing thymine-modified FcNA reporter groups were investigated further due the ability of mercuric ions (Hg2+) to bind covalently to two opposite thymine groups. Detection of these ions was possible through both cyclic voltammetry and square wave voltammetry. 3. The FcNA-conjugated DNA probes are assessed for their potential as therapeutic antisense agents by exposing the single stranded and duplexed probes to a DNase and two types of exonuclease enzyme.
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Takase, Masayoshi. "Molecular Recognition Abilities of Ferrocene-Modified Multitopic Receptors." 京都大学 (Kyoto University), 2003. http://hdl.handle.net/2433/149097.
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Hopkins, Peter K. "Novel tripodal ligands designed to complex anions." Thesis, University of Oxford, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.249200.
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Zehnder, Ralph. "Polynuclear metallocene complexes incorporating ansa-chromocene and ferrocene units." [S.l. : s.n.], 2002. http://deposit.ddb.de/cgi-bin/dokserv?idn=96652683X.
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Resendes, Rui. "Ring-opened poly(ferrocene)s, new directions and applications." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape2/PQDD_0015/NQ53681.pdf.
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Neidlinger, Andreas [Verfasser]. "Ferrocene-phenol conjugates – secondary structures and reactivity / Andreas Neidlinger." Mainz : Universitätsbibliothek Mainz, 2017. http://d-nb.info/1126763152/34.
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Allison, Matthew Steven. "Heterobimetallic ruthenium complexes containing ferrocene as anti-cancer agents." Thesis, University of Leeds, 2018. http://etheses.whiterose.ac.uk/20629/.
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This thesis details the synthesis and characterisation of ruthenium metal complexes containing functionalised ferrocene β-diketonate ligands. The anticancer and antimicrobial potential of these complexes has been explored and structural activity relationships investigated through further mechanistic investigations. A library of functionalised ferrocene β diketonate ligands were synthesised and used in the formation of two libraries of ruthenium complexes. The first series of complexes consist of organometallic ruthenium(II) arene complexes and the second series comprising of ruthenium(II) bis-bipyridyl coordination complexes. Detailed synthetic routes are outlined and all complexes are fully characterised by 1H NMR spectroscopy, 13C [1H] NMR spectroscopy, mass spectrometry and elemental analysis. X-ray crystallographic data was obtained when possible. The complexes were screened for their activity against one healthy and two cancerous cell lines; the ruthenium arene complexes were found to be highly selective towards the cancerous cell lines while the ruthenium bis-bipyridyl complexes were found to possess potent toxicity towards all cell lines. Selected complexes from each series were then studied in a low oxygen environment which caused a reduction in the cytotoxicity of the complexes. The antibacterial and antifungal properties of the two series of ruthenium complexes has also been assessed. Mechanistic studies have been conducted on selected complexes in the form of hydrolysis, hydrophobicity, biomembrane CV and comet assay in order to deduce a possible mechanism of action and mode of transport of these complexes.
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Mulas, Andrea. "Ferrocene-based chiral monomers and oligomers for sensing applications." Thesis, University of Birmingham, 2013. http://etheses.bham.ac.uk//id/eprint/4154/.
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Chiral sensing is a challenging field for the chemist. Not many sensors for chiral recognition have been studied, and only a few examples of electrochemical chiral sensors are known in the literature. The aim of this project was to synthesise novel ferrocenyl-based chiral receptors, and to study their applications for chiral sensing in solution or upon incorporation onto gold surfaces as self-assembled monolayers (SAMs). From the solution studies it was possible to gain further information on the electrochemical behaviour of ferrocenyl-based receptors during the sensing of chiral carboxylates. The incorporation of receptors onto electrode surfaces led to an economy on the amount of compound required and higher sensitivity in analyte detection. However, the chiral recognition properties and the stability of the SAMs still need to be improved. Multifunctional receptors containing BINOL and ferrocenyl reporting groups were investigated to compare the use of electrochemistry and fluorescence spectroscopy in the chiral recognition of carboxylic acids, amino acid derivatives, or amino acid anions. Finally, a DNA analogue in which ferrocenyl units were incorporated in the backbone was studied. The electrochemical properties of this system as a single strand and in its interaction with complementary strands of DNA and PNA were investigated.
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Boissonnet, Michel-Franck. "Hydrogen-bonding ferrocene derivatives for molecular recognition and organocatalysis." Thesis, University of Birmingham, 2015. http://etheses.bham.ac.uk//id/eprint/6121/.
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The aim of this project was to prepare novel ferrocene-based Hydrogen-bonding receptors and to study them in the electrochemical sensing of neutral compounds and in organocatalysed transformations. The synthesis and characterisation of 2-ferrocenyl oxazoles via gold chemistry to access a new H-bonding motif for electrochemical sensing was successfully achieved. However the targeted structure bearing a secondary amine at the 4-position of the oxazole, was found to be highly unstable and unsuitable for sensing applications. Further studies on ferrocene-based H-bonding systems towards their application in asymmetric organocatalysis were also carried out. Different chiral and achiral ferrocene-(thio)ureas were prepared and tested in four organic reactions. Their performances in the Henry and in the Morita-Baylis-Hillman reactions gave acceptable yields but did not show significant enantioselectivities. A bi-functional ferrocene-thiourea was found to be effective in the enamine co-catalysed aldol reaction of acetone and \(trans-β\)-nitrostyrene, and in the double Michael cycloaddition of ω-nitropentenoate methyl and \(trans-β\)-nitrostyrene, leading to a tetrasubstituted cyclopentane. The H-bonding properties of the ferrocene-(thio)ureas with carboxylates was also studied by \(^1\)H NMR spectroscopy. Finally, approaches towards the preparation of ferrocene-based boronate-ureas were investigated.
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Herbert, Simon Anthony. "Oxazoline directed lithiation of Calix[4]arene and Ferrocene." Thesis, Stellenbosch : Stellenbosch University, 2011. http://hdl.handle.net/10019.1/17867.
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Thesis (PhD)--Stellenbosch University, 2011.ENGLISH ABSTRACT: The use of chiral oxazoline directed lithiation provides a highly diastereoselective (up to >99% de) route to meta functionalised inherently chiral calixarenes. This methodology can be used on both the butylated and debutylated calixarene systems and is tolerant of a wide range of different electrophillic quenches allowing access to a structurally diverse range of inherently chiral metafunctionalised calixarenes. The oxazoline directing group can be removed via hydrolysis, generating a range of functionalised calixarene carboxylic acids in high ee. We also demonstrate that the use of derivative alkyllithiums such as cyclopentyl lithium can provide significantly enhanced diastereoselectivity over the conventional organolithiums such as sec-butyl lithium, when employed in ortholithiation reactions of this nature. The differences in diastereoselectivity associated with the different alkyllithiums can be tied, in certain cases, to the steric bulkiness associated with the individual reagents. In this regard we have found that the use of the so called Tolman angle or cone angle approach allows quantification of the relative steric bulk of the alkyllithium. We also detail that the oxazoline directing group provides a hitherto unknown ability to be diastereoselectively tuned through the choice of the ligand system in the ortholithiation reaction. In this regard the development of a series of diglyme based ligands have proved to provide a highly diastereoselective means of inverting the chirality from that which the use of the conventional TMEDA ligand is able to generate (up to –92% de). The use of diglyme ligands to invert the sense of chirality is also shown to occur on the ferrocenyloxazoline system and presents an apparently general and hitherto unknown facet of asymmetric oxazoline directed ortholithiation. This diglyme induced inversion has been shown to be controlled through a secondary nitrogen coordinated mechanism that is able to operate with chiral oxazolines.
AFRIKAANSE OPSOMMING: Die gebruik van chirale oksasoliengerigte litiëring verskaf ’n hoogs diastereoselektiewe (tot en met >99% do) roete om metagefunksionaliseerde, inherente chirale calixareen produkte te sintetiseer. Deur gebruik te maak van verskillende elektrofiele kan die metodologie toegepas word op beide gebutileerde en de-gebutileerde calixareen sisteme om ’n reeks uiteenlopende inherente chirale, meta-gefunksionaliseerde calixareen produkte te vorm. Die oksasolien groep kan daarna verwyder word deur hidroliese om ’n reeks gefunksionaliseerde calixareenkarboksielsure te vorm in baie hoë eo. Ons het ook gedemonstreer dat die gebruik van afgeleide alkiel-litiums, soos siklopentiel-litium, kan bydrae tot aansienlik verhoogde diastereoselektiwiteit as dit vergelyk word met meer algemene organolitiums soos sekbutiellitium, tydens ortolitiëring reaksies van hierdie natuur. Die verskille in diastereoselektiwiteit kan verbind word, in sekere gevalle, tot die steriese bonkigheid van die individuele reagense. Deur gebruik te maak van die sogenaamde Tolmanhoeke of die koniesehoek benadering is dit moontlik om die relatiewe steriese bonkighied van alkiellitiums te kwantifiseer. Daar was ook bepaal dat die oksasoliengroep die ongekende vermoë besit om die diastereoselektiwiteit van die produk te stem deur die keuse van verskillende ligand sisteme tydens die ortolitiëring reaksie. Daar was bepaal dat die chiralitiet van die produkte omgekeer kan word op ’n hoogs diastereoselektiewe manier, deur gebruik te maak van ’n reeks ontwikkelde diglymegebaseerde ligande, indien dit vergelyk word met die produkte wat deur die konvensionele TMEDA gegenereer was (tot en met –92% do). Die gebruik van diglyme ligande was ook getoets op ferroseenoksasolien sisteme en dit was bevind dat dieselfde omkering in chiraliteit ook plaasvind wat aanleiding kan gee tot 'n oënskynlik algemene en tot nou toe onbekende faset van asimmetriese oksasoliengerigte orto-litiëring. Dit is bepaal dat hierdie diglyme geïnduseerde omkering in chiraliteit beheer word deur middel van 'n sekondêre stikstofgekoördineerde meganisme, wat in staat is om saam te werk met chirale oksasoliene.
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Caniparoli, Ulysse. "Ferrocene-Based Chiral Catalyst Design for Enantioselective Cycloadditions Reactions." Doctoral thesis, Universitat Rovira i Virgili, 2021. http://hdl.handle.net/10803/672970.
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Aquesta tesi descriu el disseny i la síntesi d’una nova classe de lligands basats en ferrocè, i la seva aplicació a la catàlisi enantioselectva amb Au(I). Aquests lligands han estat específicament implementats per superar les dificultats de la catàlisi enantioselectiva amb Au(I) a causa de la separació espacial entre la informació quiral del lligand i el centre actiu localitzat a la cara oposada del metall. S’ha desenvolupat una síntesi modular d’1-(2’-dialquilarilfosfina)-3-arilferrocè, permetent l’accés a una família de complexes quirals d’Au(I) amb diferents propietats estèriques i electròniques. S’ha identificat un complex quiral d’Au(I) com a catalitzador per la cicloaddició [4+2] formal d’1,6-arilenins amb elevats rendiments i bones enantioselectivitats. El mode d’acció del catalitzador ha estat estudiat computacionalment, trobant-se que una interacció atractiva no covalent entre el lligand i el substrat és crucial per assolir una elevada inducció enantiomèrica.
Així mateix, hem aplicat un complex d’Au(I), amb un lligand fosfina que inclou una pirrolidina quiral 2,5-disustituida amb simetria C2 a una posició remota, a la síntesi de ferrocens amb quiralitat planar mitjançant una reacció d’hidroarilació de (2-alquinilaril)ferrocens.La presente tesis describe el diseño y la síntesis de una nueva clase de ligandos basados en ferroceno, y su aplicación en catálisis enantioselectiva con Au(I). Estos ligandos han sido específicamente implementados para superar las dificultades de la catálisis enantioselectiva con Au(I) debido a la separación espacial entre la información quiral en el ligando y el centro activo localizado en la cara opuesta del metal. Se ha desarrollado una síntesis modular de 1-(2’-dialquilarilfosfina)-3-arilferroceno, permitiendo el acceso a una familia de complejos quirales de Au(I) con diferentes propiedades estéricas y electrónicas. Se identificó un complejo quiral de Au(I) como catalizador para la cicloadición [4+2] formal de 1,6-arileninos con elevados rendimientos y buenas enantioselectividades. El modo de acción de nuestro catalizador quiral se ha estudiado computacionalmente, encontrándose que una interacción atractiva no covalente entre el ligando y el sustrato es crucial para lograr una elevada inducción enantiomérica. Asimismo, hemos aplicado un complejo de Au(I), cuyo ligando fosfina incluye una pirrolidina quiral 2,5-disustituida con simetría C2 en posición remota, a la síntesis de ferrocenos con quiralidad planar mediante una reacción de hidroarilación de (2-alquinilaril)ferrocenos.
This thesis describes the design and synthesis of a new class of ferrocene-based ligands applied to enantioselective gold(I) catalysis. These ligands have been specifically implemented to overcome difficulties of enantioselective gold(I) catalysis due to the spatial separation between the chiral information on the ligand and the catalytic site located on the opposite side of the metal center. A modular synthesis of 1-(2’-dialkylarylphosphine)-3-arylferrocene was developed allowing to access a family of chiral gold(I) complexes bearing various steric and electronic properties. One chiral gold(I) complex was identified to catalyze the formal [4+2] cycloaddition of 1,6-arylenynes in high yields and good enantioselectivities. The working mode of our chiral catalysts was studied computationally. An attractive non-covalent interaction between the ligand and the substrate was found to be crucial to achieve high enantioinduction. Additionally, we applied a phosphine-supported gold(I) complex containing a chiral remote C2-symmetric 2,5-disubstituted pyrrolidines to the enantioselective synthesis of planar chiral ferrocenes by hydroarylation of (2-alkynylaryl)ferrocenes.
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MALEZIEUX, BERNARD. "Chiralite plane en chimie du ferrocene et du benchrotrene." Paris 6, 1995. http://www.theses.fr/1995PA066152.
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Ce travail est constitue de deux parties ayant pour trait commun la chiralite plane. La premiere porte sur la synthese d'analogues ferroceniques de l'hexestrol. Cette synthese necessite la resolution de trois elements de chiralite: une plane et deux centrees. Le probleme a ete resolu via la preparation d'amino-alcools ferroceniques optiquement actifs obtenus par l'action du lithien optiquement actif du dimethylaminomethylferrocene sur une benzyle cetone. Des derives ont ete obtenus a partir des amino-alcools precurseurs et sont decrits dans cette these. La seconde partie illustre la synthese enantiogenique d'hetero-diesters d'arene chrome tricarbonyle par voie enzymatique
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Wang, Lixin. "Ferrocene-based molecular electronics and nanomanufacturing of palladium nanowires." College Park, Md. : University of Maryland, 2007. http://hdl.handle.net/1903/7757.
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Thesis (Ph. D.)--University of Maryland, College Park, 2007.Thesis research directed by: Dept. of Chemistry and Biochemistry. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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Magnani, Maurizio. "Polimeri metacrilici contenenti ferrocene: sintesi mediante ATRP e proprietà." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2014. http://amslaurea.unibo.it/6545/.
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An investigation on the synthesis and properties of ferrocene-containing methacrylate monomer and polymer was carried out. Block copolymers of Ferrocenylmethyl Methacrylate with methyl, butil and esil methacrylate, were also prepared. The side-chain ferrocene-containing polymers and copolymers were prepared via atom transfer radical polymerization (ATRP). The glass transition temperature (Tg) values of the polymers and copolymers were measured by differential scan calorimetry (DSC).The thermal degradation behavior of copolymers was also studied and compared with the respective homopolymers. Cyclic voltammetry was employed to study the electrochemical properties. Preliminar electrochemical studies with a glassy carbon and Indium Tin Oxide electrodes modified with ferrocene-polymer conducted in aqueous and organic media are reported.
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Beskeni, Rhoda. "Synthesis of staggered triphenylene twins linked through ferrocene bridges." Thesis, University of East Anglia, 2016. https://ueaeprints.uea.ac.uk/63359/.
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The main target of this research was to investigate strategies for linking triphenylene discogens via staggered, ferrocene links. The thesis begins with a general introduction to liquid crystals and triphenylenes. The results of this research are then described. In the first part, a new and improved synthesis of dibromotriphenylene intermediates is described. The new procedure allows convenient access to the material without extensive chromatography. Attempts to couple dibromotriphenylenes with ferrocene derivatives is then discussed using ferrocene boronic acid and via acetylene links (Sonagashira couplings). Unfortunately, the required twinned structures were not observed, but a number of new monomeric derivatives (Ferrocenyl triphenylenes) were isolated. The reactions of ethynyl triphenylenes were complicated by efficient and competing homocoupling. The remainder of the thesis describes a changed strategy whereby triphenylenes were linked via ester bridges. The molecular geometry was varied by linking monohydroxytriphenylene through 1,1’- ferrocene dicarboxylic acid plus three isomeric phthalic acids. The mesophase behaviour of the new materials is described.
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Halstead, Joshua M. "Oxidation of Ferrocene Derivatives with Dibenzoyl Peroxide and meta-Chloroperoxybenzoic Acid." Cleveland State University / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=csu154278958361703.
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Gupta, Deepshikha. "NEW APPROACHES TO CYCLOPENTADIENYL-FUSED THIOPHENE COMPLEXES OF IRON and SYNTHESIS AND CHARACTERIZATION OF CARBONIC ANHYDRASE ACTIVE-SITE MIMICS FOR CO2 HYDRATION." UKnowledge, 2018. https://uknowledge.uky.edu/chemistry_etds/92.
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Polyheterocycles such as polythiophene and its derivatives comprise an important class of conducting polymers used for electronic applications. They have been of great interest for use in electronic materials due to their increased environmental stability as well as novel electronic properties in their polymer states. We have been interested in exploring the electronic properties of organometallic analogues of the low-band-gap polymer poly(benzo[3,4-c]thiophene) (polyisothianaphthene) that incorporates η5-cyclopenta[c]thienyl monomers such as ferroceno[c]thiophene. First chapter of this dissertation involved synthetic attempts to ferroceno[c]thiophene. Exploring a shorter synthetic route to starting material, 1,2-di(hydroxymethyl)ferrocene was the first task. This was followed by attempts to synthesize an important precursor, 1,3-dihydroferroceno[c]thiophene to our target molecule, ferroceno[c]thiophene. In order to achieve our target precursor molecule, 1,3-dihydroferroceno[c]thiophene, we reacted 1,2-di(hydroxymethyl)ferrocene with H2S/H2SO4 and Na2S/HBF4 respectively. Reaction of 1,2-di(hydroxymethyl)ferrocene with either H2S/H2SO4 or Na2S/HBF4 results in 2,16-dithia[3.3](1,2)ferrocenophane instead of monomeric 1,3-dihydroferroceno[c]thiophene. Dehydration of 1,2-di(hydroxymethyl)ferrocene with dilute H2SO4 resulted in 2,16-dioxa[3.3](1,2)ferrocenophane. Formation of the five-membered tetrahydrothiophene or tetrahydrofuran rings is probably disfavored compared to formation of the ten-membered ferrocenophane rings because of greater strain in the five-membered rings. Thus, in order to achieve our target molecule ferroceno[c]thiophene, we took an alternate route. We decided to pursue the route with 1,4-dihydro-2,3-ferrocenodithiin being the precursor to our final target molecule. This was successfully accomplished. 1,2-Di(hydroxymethyl)ferrocene reacts with thiourea in the presence of catalytic trifluoroacetic acid to give a water-soluble thiouronium salt, which reacts with aqueous potassium hydroxide in air to give 1,4-dihydro-2,3-ferrocenodithiin, via oxidation of the intermediate 1,2 di(mercaptomethyl)ferrocene. 1,4-dihydro-2,3-ferrocenodithiin, an important precursor to our desired heterocyclic chemistry was synthesized.
The increased emission of CO2, a greenhouse gas, to the atmosphere is a matter of serious worldwide concern. Every year a few gigatons of CO2 are added to the atmosphere by various anthropogenic activities like burning of fuel for electricity, running industry and transportation. Thus, developing ways to reduce the emission of CO2 to the atmosphere is of major importance. Although the amine-based absorption method is considered the most reliable, it is an expensive alternative. The catalyzed enhancement of CO2 absorption is a critical component to reduce the capital cost of CO2 capture. Specifically, an effective catalyst will increase the CO2 hydration rate, thereby decreasing the size of the absorber tower needed. In biological systems, CO2 hydration is catalyzed by the enzyme carbonic anhydrase, which contains ZnII in its active site. Carbonic anhydrase typically is not stable enough to be used in an industrial process, therefore, there is a need to synthesize robust, inexpensive CO2 hydration catalysts.
Majority work of this dissertation focuses on designing catalysts that show high CO2 hydration rate similar to carbonic anhydrase while showing superiority towards temperature, pH and inhibitors. We focused our efforts on complexes of Zn, Cu and Co with ligands such as 1,4,7,10-tetraazacyclododecane (cyclen), 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (teta and tetb), tris(benzimidazolylmethyl)amine (BIMA) and anionic tris(pyrazolylborate)s that mimic the enzyme, carbonic anhydrase. Several of these complexes have been reported for their interesting CO2 capture properties but they contain hazardous perchlorate ion. We desired to replace them with benign, non-coordinating counterions like PF6-, BF4-, Cl-, CH3COO-, NO3-, CF3SO3-, SiF62- that avoid the potentially explosive perchlorate salts. In order to test the activity of synthesized catalysts under industrial capture conditions, we designed a quick experimental screening pH drop method. [[Zn(cyclen)(H2O)][SiF6]•2H2O as well as a number of other catalysts have been synthesized and tested for their post-combustion CO2 capture enhancement capabilities in aqueous solvent mixtures under both pH-drop screening and stopped-flow conditions.
[Zn(cyclen)(H2O)][SiF6]•2H2O, which has an unreactive counteranion, is found to catalyze CO2 hydration in aqueous solvent mixtures under both pH-drop screening and stopped-flow conditions. However, under pH-drop which has conditions similar to industrial post combustion capture, activity of Zn(cyclen)(H2O)][SiF6]•2H2O drops as compared to observed in stopped-flow conditions probably because of bicarbonate coordination to Zn active site in these systems. The Zn center is highly electron deficient and therefore easily coordinates anions, inhibiting the ability to reform hydroxyl species on the metal. Thus, we decided to test the catalysis of benchmark enzyme carbonic anhydrase under similar conditions to determine the threshold value. Carbonic anhydrases catalyze the hydration of carbondioxide at ambient temperatures and physiological pH with the highest known rate constant= 106 M–1 s–1, but in our system (CAER pH drop screening) came out to be 438797 M–1 s–1. The lower catalytic rate constant for carbonic anhydrase in 0.1000 M K2CO3, similar to Zn-cyclen, strengthens the conjecture that at high bicarbonate concentrations, HCO3– binding to the Zn(II) active site slows catalysis by inhibiting bicarbonate displacement with water to regenerate the active species.
The complexes containing anionic ligands that donate electron density into the metal center may serve to remove anionic bicarbonates/carbamates from the secondary coordination sphere and away from the metal center, thereby facilitating bicarbonate/anion dissociation and increasing CO2 hydration rates. We studied catalysis of trispyrazolylborate molecule in 30% MEA and found the molecule to be catalytically active. We also developed an NMR-based method to see if the coordination of solvents to CO2 capture solvents can be studied.
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Ratera, Bastardas Imma. "Ferrocene-Based Polychlorotriphenylmethyl radical: A new approach towards multiproperty materials." Doctoral thesis, Universitat Autònoma de Barcelona, 2002. http://hdl.handle.net/10803/3149.
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Al llarg d'aquesta tesi com a part del esforç general per tal d'extendre el nombre de materials moleculars que combinin dues o més propietats en la mateixa molècula, s'ha desenvolupat la síntesi i caracterització d'una nova sèrie de metal.locens (ferrocens i rutenocens) connectats a mono-bi- i tri- radicals polyclorotrifienilmetílics els quals han provat que realment és possible de modular les seves propietats mitjançant el canvi de capacitats donadores dels metalocens, de capacitats acceptores de les unitats radicalàries així com també el canvi del pont. S'han estudiat les propietats magnètiques dels diferents mono- bi- i tri- radicals mitjançant les tècniques d'EPR i SQUID. A partir de les dades obtingudes pels biradicals estudiats, es pot concloure que el pont 1,1'-ferrocenilè actua com a acoblador ferromagnètic entre les dues unitats radicalàries connectades a ell. Quan el ferrocè és substituït amb grups metílics o bé és substituït per un rutenocè, l'acoblament magnètic entre les dues unitats radicalàries desapareix mostrant-se un comportament paramagnètic al llarg de tot el rang de temperatures mesurat. A partir de les dades de susceptibilitat magnètica dels monoradicals s'obtenen valors de magnetització molt alts a temperatura ambient els quals són un indici de la significant contribució orbitàlica de la fracció de Fe (III) per sobre del valor del spin orgànic sol. Aquest resultat suggereix un fenomen de transferència electrònica intramolecular entre el ferrocè i la unitat radicalària. A més a més, per un dels monoradicals sintetitzats, també se n'ha estudiat la isomerització trans - cis tant tèrmica com fotoinduïda mitjançant la tècnica de UV/Vis, ESR spectrosocopy així com també de cromatografia d'HPLC. Aquesta isomerització genera un procés d'autoassemblatge induït tan tèrmica- com fotoquímicament d'un sol sentit i representa un exemple molt interessant d'un sistema fotomagnètic basat en un fenomen supramolecular en el qual una espècie doblet es convertida a una espècie singlet.
Aquesta família de radicals policlorotrifenilmetílics units a un ferrocè també presenten un fenomen de transferència electrònica intramolecular del qual se'n pot modular la seva energia fàcilment mitjançant el canvi de substituents de la unitat donadora, acceptora o fins i tot canviant la naturalesa del dissolvent. Mesures d'absorció espectroscòpiques de temps de resolució de pico-segons ens han permès observar i monitoritzar per primera vegada l'espècie de càrregues separades la qual ens confirma per primera vegada el fenomen de transferència electrònica intramolecular fotoinduït. També ha estat descrit per primera vegada un nou exemple de tautomerisme de valència que combina un radical orgànic com a grup acceptor i un ferrocè com a grup donador.
Finalment, també s'ha comprovat que els radicals policlorotrifenilmetílics constitueixen un sèrie de compostos de capa electrònica oberta molt atractiva que combina elevades respostes d'ONL amb bones estabilitats químiques, tèrmiques i foto-òptiques, gràcies al seu caràcter octupolar. Els sistemes de ferrocens connectats a unitats radicalàries policlorotrifenilmetíliques també exhibeixen intenses respostes d'ONL les quals poden ser modulades mitjançant el canvi de capacitat donadora del metal.locè o accpetora del radical.
This thesis as part of a general effort aimed at extending the range of molecular materials combining two properties in the same molecule, has developed the synthesis and characterization of new series of metallocene (ferrocene and ruthenocene) based polychlorotriphenylmethyl mono, bi- and tri- radicals proving that it is possible their tuning by changing the donor ability of the metallocene unit, the acceptor ability of the radical unit and the nature of the bridge. The magnetic properties of different mono, bi and tri radicals have been studied by EPR and SQUID. From the magnetic data of the biradicals studied, it is conclude that the 1,1'-ferrocenylene bridge acts as a ferromagnetic coupler between the two radical units connected to it. When the ferrocene unit is substitute with methyl groups or it is changed for a ruthenocene unit, the magnetic exchange vanishes showing a paramagnetic behaviour in all the temperature range. From the magnetic susceptibility data for the monoradicals an outsized values of magnetization at room temperature is observed, which it is an indication of significant orbital contributions of the Fe(III) fraction over the spin value. This result suggests a temperature dependent intramolecular electron transfer phenomenon between the ferrocene and the radical unit. In addition, the thermal and photoinduced trans to cis isomerization of one of the monoradicals has been monitored by UV/Vis and ESR spectrosocopy and also followed by HPLC chromatography. This one-way thermal and photoinduced self-assembly process represents an interesting example of a photomagnetic system based on a supramolecular phenomenon in which a doublet species is converted into a singlet one.
Such ferrocene-polychlorotriphenylmethyl radicals present intramolecular electron transfer phenomenon which energy can be easily tuned by changing the substitutents of the donor or acceptor units or even the nature of the solvent. Picosecond time resolved absorption spectroscopy measurements allow us observing and monitoring for the first time the charge separation state that confirms the photoinduced electron transfer phenomena. It has also been described for the first time a novel valence tautomeric example combining an organic radical as acceptor unit and a ferrocene unit as the donor group.
Finally, it has been proved that polychlorotriphenylmethyl radicals constitute a very attractive open-shell series that combines both a high NLO response and good chemical, thermal, and photo-optical stabilities, thanks to their octupolar character. Ferrocene based polychlorotriphenylmethyl radicals systems also exhibits intense NLO responses that can be modulated at will simply tuning the donor and acceptor capabilities of the ferrocene and radical units.
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Lenze, Norman. "Neuartige Zinn- und Gallium-substituierte Ferrocene Synthese, Struktur und Eigenschaften /." [S.l. : s.n.], 2001. http://deposit.ddb.de/cgi-bin/dokserv?idn=969324057.
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Elihn, Karine. "Synthesis of carbon-covered iron nanoparticles by photolysis of ferrocene." Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis : Univ.-bibl. [distributör], 2002. http://publications.uu.se/theses/91-554-5302-3/.
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Du, Shuoren. "Towards redox control of organometallic catalysts bearing ferrocene-based ligands." Thesis, Imperial College London, 2013. http://hdl.handle.net/10044/1/23902.
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This project focuses on the design and synthesis of redox active palladium and rhodium complexes containing ferrocene moieties, and the influence of switching the oxidation state of the ligand on the catalytic behaviour of the metal centre. The redox effect on the catalyst is investigated via carbonylation, hydrogenation and Suzuki cross-coupling reactions. Chapter 1. Introduction to redox-controlled catalysis and palladium-catalyzed carbonylation reactions. The categorization of redox active ligands, and the use of electrochemistry as a tool for choosing the right chemical redox agent are discussed. The aims of the project are outlined. Chapter 2. Chemical oxidation of a series of palladium complexes containing bidentate ferrocen-1,1'-diphosphines, and their catalytic behaviour towards the carbonylation reactions of aryl halides compared with the non-oxidized complexes are reported. A hypothesis is proposed to explain the difference in the catalytic reactivities of the same complex with a different state of charge of the ligand. Chapter 3. The synthesis of a series of new bidentate ligands from ferrocenylamine and their palladium complexes is reported. The electrochemical properties of these palladium N-P complexes are described, as well as their performance as catalysts for carbonylation reactions. Chapter 4. An improved method for the purification of halogenated feorrcenes is included in this chapter. The synthesis of other groups of ferrocene-based ligands and their complexation towards new palladium N-N complexes is reported. Chapter 5. Attempts to realize redox control on other catalytic processes, such as palladium-catalyzed Suzuki cross-coupling reactions and rhodium-catalyzed hydrogenation, is discussed. Chapter 6. Conclusions and future work of this project. Chapter 7. Experimental details. References are included in each of these chapters.
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Krauße, Nico [Verfasser]. "Ausgedehnte [pi]-Systeme auf Basis 1,1'-disubstituierter Ferrocene / Nico Krauße." Hannover : Technische Informationsbibliothek und Universitätsbibliothek Hannover (TIB), 2014. http://d-nb.info/1049227972/34.
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Al, Khalyfeh Khaled. "Ferrocene-Based Monomers, Oligomers and Polymers as Electro-Active Materials." Doctoral thesis, Universitätsbibliothek Chemnitz, 2016. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-216647.
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The present PhD thesis deals with the synthesis and characterization of functionalized ferrocenes with up to four aldehyde and vinyl groups and their usage as monomers to produce novel ferrocene-based oligomers with conjugated backbones via ADMET (acyclic diene metathesis) and HWE (Horner-Wadsworth-Emmons) reaction protocols. In addition, ferrocene-containing polymers (linear, cross-linked and co-polymers) with aliphatic backbones generated by anionic bulk and solution polymerization routes, and their electrochemistry behaviors were studied. The main aspects of this work lies in the enhancement of the electrical properties of the ferrocene-based materials (oligomers or polymers) by varying the polymer backbone, providing multi-functionalities for cross-linking and co-polymerization processes and thereby increasing the molecular weight of the products, furthermore, the application as electro-active materials, especially for the charge storage purposes is discussed. High monomer consumption, relatively high molar mass as well as longer chains were achieved by bulk protocol. Electrochemical measurements (CV) reveals that formyl-ferrocenes bearing more than two formyl functionalities are very electron poor materials and easily decomposes upon oxidation. Reducing the measurement temperature and the usage of [NnBu4][B(C6F5)4] as electrolyte allowed for reliable behavior. A linear correlation between the redox potential and the number of the formyl functionalities was found. Multicyclic measurements showed that ferrocenyl / ferrocenium redox couples in the polymeric materials are stable at least up to 100 cycles. The spectro-electrochemical studies show that the conjugated materials (oligomers) have electron transfer interactions (IVCT) through the chains, while the aliphatic backbone between the ferrocenyl units (poly vinylferrocene materials) hindered the metal-metal coupling along the chain and only a ligand-to-metal charge transfer excitation could be observedDie vorliegende Doktorarbeit beschäftigt sich mit Synthese und Charakterisierung von funktionalisierten Ferrocenen mit bis zu vier Aldehyd- und Vinylgruppen und ihrer Verwendung als Monomere für neuartige ferrocenbasierte Oligomere mit konjugiertem Rückgrat unter ADMET (acyclic diene metathesis) und HWE- (Horner-Wadsworth-Emmons) Reaktionsbedingungen. Zusätzlich wurden ferrocenhaltige Polymere mit einem aliphatischen Rückgrat durch Polymerisation mit und ohne Lösemittel hergestellt und ihr elektrochemisches Verhalten untersucht. Das Hauptaugenmerk dieser Arbeit liegt in der Optimierung der elektrochemischen Eigenschaften der ferrocenbasierten Materialien (Oligomere oder Polymere) durch Variation des Polymerrückgrats, welche zahlreiche funktionelle Gruppen für die vernetzte Polymerisation und die Co-Polymerisation liefert. Durch diesen Prozess wird das molekulare Gewicht erhöht. Zusätzlich wird die Verwendung als elektroaktive Materialien insbesondere für die Energiespeichertechnik diskutiert. Durch lösungsmittelfreie Reaktionsbedingungen wurden ein hoher Monomerumsatz, relativ hohe molare Massen und zugleich längere Polymerketten erzielt. Elektrochemische Messungen (CV) zeigten, dass Ferrocenmoleküle mit mehr als zwei Formylgruppen die Elektronendichte an der Ferrocenyleinheit verringern und bei Oxidation leicht zersetzt werden. Erniedrigung der Messtemperatur und die Verwendung des nur schwach koordinierenden Leitsalzes [NnBu4][B(C6F5)4] führten zu aussagekräftigen Ergebnissen. Weiterhin konnte ein linearer Zusammenhang zwischen dem Redoxpotential und der Anzahl der Formyleinheiten aufgezeigt werden. Mutlizyklische Messungen bestätigten, dass das Ferrocen / Ferrocenium-Redoxpaar mindestens 100 Zyklen stabil ist. Mittels spektroelectrochemisches Messungen konnte gezeigt werden, dass konjungierte (oligomere) Verbindungen eine elektronische Wechselwirkung (IVCT) aufweisen, während aliphatische Rückgrade eine Wechselwirkung zwischen Ferrocen / Ferrocenium (polyvinylferrocenbasierte Materialien) verhindern und nur ein LMCT Übergang (Ligand zu Metall Charge-Transfer) beobachtet werden kann
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Frison, Gilles. "Du phosphinidene au ferrocene : un dialogue entre experience et theorie." Paris 6, 2000. http://www.theses.fr/2000PA066175.
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Cette these illustre la complementarite des approches experimentale et theorique dans le cas de l'etude d'especes insaturees du phosphore. Au cours du premier chapitre, nous presentons les differentes methodes theoriques utilisees au cours de ce travail, et en particulier l'analyse topologique de la fonction de localisation des electrons (elf). Deux classes de composes ont ensuite ete examinees. Dans un premier temps, nous nous sommes interesses au phosphinidene p-r. Le chapitre ii presente une etude theorique de la structure electronique des molecules obtenues lors de la coordination de p-r sur des fragments organiques (diaminocarbenes) et organometalliques. En se basant sur les resultats obtenus, nous avons envisage la modification de la reactivite electrophile du complexe de pentacarbonyltungstene du phosphinidene en procedant a des substitutions de ligands carbonyles ou du substituant du phosphore (chapitre iii). Ces travaux nous ont amenes a synthetiser differents cyclopentadienyl- et ferrocenylphospholes. Ceux-ci ont alors oriente notre interet vers une deuxieme classe de composes, les complexes presentant une coordination eta-5 (chapitre iv). En effet, la reaction de migration sigmatropique 1,5 sur les phospholes precedemment obtenus permet la synthese de nouveaux composes (phospholyle, phosphaferrocene, 1-phosphanorbornadiene, 1,1-biphosphole) presentant une substitution originale. Une description theorique des interactions metal-cycle a ete de plus effectuee, en particulier afin d'analyser l'influence de l'introduction d'un atome de phosphore dans ces systemes.
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Eralp, Tugce. "Synthesis Of Ferrocenyl Quinones And Polyquinanes." Master's thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/3/12606205/index.pdf.
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ABSTRACT
SYNTHESIS OF FERROCENYL QUINONES AND POLYQUINANES
Eralp, Tugçe M.S., Department of Chemistry Supervisor: Assoc. Prof. Dr. Metin Zora June 2005, 79 pages With the discovery of antitumor activity of ferrocene derivatives, research on new ferrocene derivatives have gained importance. For this purpose, we have investigated the synthesis of ferrocenyl quinones starting from squaric acid. Several quinone derivatives are known to have antitumor and antibiotic activities. In this research, by combining ferrocene and quinone moieties, we have targeted ferrocenyl quinones which are supposed to have enhanced potential antitumor activity. Thermolysis of ferrocenyl-substituted 4-alkynyl cyclobutenones, which have been prepared from ferrocenyl cyclobutenediones and alkynyllithiums, leads to the formation of ferrocenyl quinones and besides also cyclopentendiones are observed. Ferrocenyl cyclobutenediones have been prepared from known cyclobutenediones by nucleophilic addition of ferrocenyllithium followed by hydrolysis. A mechanism for the formation of ferrocenyl substituted quinones, involving first electrocyclic ring opening of alkynyl substituted cyclobutenone to ketene intermediate and then ring closure, has been proposed. Polyquinanes are widely found in nature and proved to have biological activity such as antibiotic activity. For the synthesis of ferrocenyl polyquinanes, starting from squaric acid, ferrocenyl substituted cyclobutenediones were prepared and reacted with alkenyllithium, and hydrolyzed to afford ferrocenyl substituted polyquinanes. A mechanism has been proposed that involves first the formation of cis- and trans-divinyl substituted cyclobutenes that produce cyclooctatriene-dienolate, upon hydrolysis of this dienolate, aldol-type transannular ring closure reaction takes place, producing polyquinanes.
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Han, Nam Fong. "Soluble and polymer-bound palladium and platinum complexes of ferrocene derivatives." Thesis, University of British Columbia, 1986. http://hdl.handle.net/2429/27312.
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The preparation, characterization, and catalytic properties of some soluble and polymer-bound palladium and platinum complexes of ferrocene derivatives are described. Special emphasis has been placed on studies of the mixed "hard-soft" ligands such as PPFA and ISOPFA. [Formula Omitted]
The soluble complexes (L-L)MC1₂ (L-L = BPPF, PPFA, ISOPFA, BPPFA; M = Pd, Pt) and [(L-L)PdS₂][C10₄]₂ (L-L = BPPF, PPFA; S = DMF, py) have been characterized by microanalyses, NMR and IR spectroscopic techniques.
The cationic palladium(II) complex [(L-L)PdS₂][C10₄]₂ (L-L = PPFA, S = DMF) is an effective catalyst precursor for the hydrogenation of simple olefins at 30°C and 1 atm pressure. The rate of styrene hydrogenation
depends on the substrate concentration, catalyst concentration and the solvent. The results are consistent with a homogeneous catalytic system. Platinum(II) complexes (L-L)PtCl₂ (L-L = (S,R)-PPFA, (S,R)-ISOPFA) are effective catalyst precursors for the hydrosilylation of aromatic ketones with Ph₂SiH₂. The complexes with mixed "hard-soft" ligands are better catalyst precursors than those with di(tertiary phosphine) ligands. Under the same conditions the hydrosilylation of ferrocenyl ketones results in further reduction and affords mainly the alkylferrocene products. The stable carbonium ion FcC⁺HCH₃ (Fc = Fe-(C₅H₅)(C₅H₄)-) is reduced by Ph₂SiH₂ to FcCH₂CH₃ in a thermal reaction which is catalyzed by the complex (PPFA)PtCl₂. The reaction of Ph₂SiH₂ with (L-L)PtCl₂ (L-L = PPFA, ISOPFA) yields a stable platinum(IV) hydride, which eliminates Ph₂SiHCl in solution to afford (L-L)PtHCl. The mechanistic implications of these observations are discussed.
Polymers functionalized with ferrocene and ferrocene derivatives
have been prepared. Mossbauer spectroscopic techniques and microanalyses
are used to characterize these polymers and their palladium and platinum
complexes. In a number of cases these results are confirmed by the cross-polarization/magic-angle spinning ¹³C NMR spectroscopic technique.
The palladium(II) and platinum(II) derivatives of the ferrocenyl-amine and -phosphine containing polymers are effective catalysts for the hydrogenation and hydrosilylation of olefins. All the catalysts can be easily separated from the reaction mixture and can be recycled with no loss of activity. The pronounced effect of the attached ligand in the palladium based polymers indicates that free metal is not involved.
However, in the case of platinum based catalysts, it is likely that reduction to platinum metal takes place.Science, Faculty of
Chemistry, Department of
Graduate
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Saku, Duduetsang. "Synthesis and characterization of symmetrical and unsymmetrical ferrocenyl ligands for use in the preparation of Redox Active Ruthenium Alkylidene Complexes." Thesis, Nelson Mandela Metropolitan University, 2007. http://hdl.handle.net/10948/701.
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Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.