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Complexes NCN de Ni(II) et Ni(III) : synthèse, caractérisation et rôle dans le mécanisme de couplage C-O, C-N et C-halogènesCloutier, Jean-Philippe 09 1900 (has links)
No description available.
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Fonctionnalisation de liaisons C(sp3)-H non activées catalysées par le palladium / Palladium catalyzed functionalization of nonactivated C(sp3)-H bondsRenaudat, Alice 04 October 2010 (has links)
La fonctionnalisation de liaisons C-H réputées peu réactives ouvre de nouvelles perspectives en synthèse organique. Une stratégie efficace consiste en l’utilisation d’un métal de transition. Les travaux de thèse présentés dans ce mémoire s’inscrivent dans ce contexte. Dans un premier temps, la réaction étudiée, catalysée par le palladium, vise à étendre une méthodologie mise au point au laboratoire, permettant la synthèse de benzocyclobutènes par activation intramoléculaire de liaisons C(sp3)-H de groupements méthyles benzyliques, à des composés non aromatiques. Plusieurs substrats ont été synthétisés pour être ensuite placés dans les conditions de la réaction d’activation C(sp3)-H, dans le but d’induire la formation du cyclobutène ou du cyclobutane désiré. Le processus n’est pas sélectif et de nombreux produits secondaires sont obtenus par des réactions péricyliques ou par des réarrangements suite à l’ouverture du palladacycle intermédiaire. Dans un deuxième temps, nos travaux ont permis de mettre à jour une nouvelle réaction de fonctionnalisation C(sp3)-H, catalysée par le palladium permettant l’arylation d’esters en position β par un mécanisme original. Les investigations portent sur l’optimisation complète de cette réaction, la compréhension du mécanisme et le développement d’une version énantiosélective prometteuse. Le mécanisme de cette réaction, confirmé par des calculs DFT réalisés en collaboration avec C. Kefalidis et E. Clot, se rapproche formellement de celui observé en α-arylation, puisqu’il repose sur la formation d’un énolate de palladium. La stratégie mise au point permet le couplage, dans des conditions douces, d’esters simples et commerciaux avec des halogénures d’aryles contenant un groupement électronégatif en position ortho, donnant ainsi accès à des intermédiaires de synthèse intéressants tels qu’un analogue de la phénylalanine ou des composés fluorés. / The direct functionalization of C-H bonds represents an atom- and step-economical alternative to more traditional synthetic methods based on functional group transformation, which often require multi-step sequences. In particular, transition-metal catalysis has recently emerged as a powerful tool to functionalize otherwise unreactive C-H bonds. In this context, we first investigated the extension of a methodology that has been developed in our laboratory for the synthesis of benzocyclobutenes via C(sp3)-H activation, to non aromatic compounds. Substrates have been synthesized in order to be evaluated in the reaction to form cyclobutenes or cyclobutanes. The process was not selective and several by-products were formed via pericylic reactions or rearrangements of the intermediate palladacycle. Our research has also focused on a conceptually new palladium catalyzed β-C-H arylation of carboxylic esters method. The investigations consisted of a complete optimization of the reaction conditions, an evaluation of the scope and elucidation of the mechanism. It was found that this type of [bêta]-arylation is mechanistically related to α-arylation because it involves the formation of a palladium-enolate. Computational studies (DFT calculations, C. Kefalidis et E. Clot) confirmed the proposed mechanism. Our strategy allowed a mild and efficient intermolecular arylation reaction from aryl halides bearing an ortho electronegative group, giving rise to a range of synthetically useful functionalized carboxylic esters such as phenylalanine analogues and new fluorinated building blocks.
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POCN-type Pincer Complexes of NiII and NiIII : synthesis, reactivities, catalytic activities and physical propertiesSpasyuk, Denis M. 08 1900 (has links)
Cette thèse décrit la synthèse, la caractérisation, les réactivités, et les propriétés physiques de complexes divalents et trivalents de Ni formés à partir de nouveaux ligands «pincer» de type POCN. Les ligands POCN de type amine sont préparés d’une façon simple et efficace via l’amination réductrice de 3-hydroxybenzaldéhyde avec NaBH4 et plusieurs amines, suivie par la phosphination de l’amino alcool résultant pour installer la fonction phosphinite (OPR2); le ligand POCN de type imine 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) est préparé de façon similaire en faisant usage de PhCH2NH2 en l’absence de NaBH4. La réaction de ces ligands «pincer» de type POCN avec NiBr2(CH3CN)x en présence d’une base résulte en un bon rendement de la cyclométalation du lien C-H situé en ortho aux fonctions amine et phosphinite. Il fut découvert que la base est essentielle pour la propreté et le haut rendement de la formation des complexes «pincer» désirés. Nous avons préparé des complexes «pincer» plan- carrés de type POCN, (POCNRR΄)NiBr, possédant des fonctions amines secondaires et tertiaires qui démontrent des réactivités différentes selon les substituants R et R΄. Par exemple, les complexes possédant des fonctions amines tertiaires ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) démontrent des propriétés rédox intéressantes et pourraient être convertis en leurs analogues trivalents (POCNR2)NiBr2 lorsque réagis avec Br2 ou N-bromosuccinimide (NBS). Les complexes trivalents paramagnétiques à 17 électrons adoptent une géométrie de type plan-carré déformée, les atomes de Br occupant les positions axiale et équatoriale. Les analyses «DSC» et «TGA» des ces composés ont démontré qu’ils sont thermiquement stables jusqu’à ~170 °C; tandis que la spectroscopie d’absorption en solution a démontré qu’ils se décomposent thermiquement à beaucoup plus basse température pour regénérer les complexes divalents ne possédant qu’un seul Br; l’encombrement stérique des substitutants amines accélère cette route de décomposition de façon significative. Les analogues NMe2 et N(morpholinyl) de ces espèces de NiIII sont actifs pour catalyser la réaction d’addition de Kharasch, de CX4 à des oléfines telles que le styrène, tandis qu’il fut découvert que l’analogue le moins thermiquement stable (POCNEt2)Ni est complètement inerte pour catalyser cette réaction.
Les complexes (POCNRH)NiBr possédant des fonctions amines secondaires permettent l’accès à des fonctions amines substituées de façon non symétrique via leur réaction avec des halogénures d’alkyle. Un autre avantage important de ces complexes réside dans la possibilité de déprotonation pour préparer des complexes POCN de type amide. De telles tentatives pour déprotoner les fonctions NRH nous ont permis de préparer des espèces dimériques possédant des ligands amides pontants. La nature dimérique des ces complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 et Ph) fut établie par des études de diffraction des rayons-X qui ont démontré différentes géométries pour les cœurs Ni2N2 selon le substituant N : l’analogue (PhCH2)N possède une orientation syn des substitutants benzyles et un arrangement ressemblant à celui du cyclobutane du Ni et des atomes d’azote, tandis que l’analogue PhN adopte un arrangement de type diamant quasi-planaire des atomes du Ni et des atomes d’azote et une orientation anti des substituants phényles. Les espèces dimériques ne se dissocient pas en présence d’alcools, mais elles promouvoient l’alcoolyse catalytique de l’acrylonitrile. De façon intéressante, les rendements de ces réactions sont plus élevés avec les alcools possédant des fonctions O-H plus acides, avec un nombre de «turnover» catalytique pouvant atteindre 2000 dans le cas de m-cresol. Nous croyons que ces réactions d’alcoolyse procèdent par activation hétérolytique de l’alcool par l’espèce dimérique via des liaisons hydrogènes avec une ou deux des fonctions amides du dimère.
Les espèces dimériques de Ni (II) s’oxydent facilement électrochimiquement et par reaction avec NBS ou Br2. De façon surprenante, l’oxydation chimique mène à l’isolation de nouveaux produits monomériques dans lesquels le centre métallique et le ligand sont oxydés. Le mécanisme d’oxydation fut aussi investigué par RMN, «UV-vis-NIR», «DFT» et spectroélectrochimie. / This thesis describes the synthesis, characterization, reactivities, and physical properties of divalent and trivalent complexes of Nickel based on new POCN-type pincer ligands. The amino-type POCN ligands were prepared in a simple and efficient manner via reductive amination of 3-hydroxybenzaldehyde with NaBH4 and various amines, followed by phosphination of the resulting amino alcohol to install the phosphinite (OPR2) functionality. The imino-type POCN ligand 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) was prepared similarly using PhCH2NH2 in the absence of NaBH4. Reaction of these POCN-type pincer ligands with NiBr2(CH3CN)x in the presence of a base results in the high yield cyclometalation of the C-H bond which is ortho to the amine and phosphinite functionalities.
The base was found to be essential for a clean and high yield formation of the desired pincer complexes. We have thus prepared square planar POCN-type pincer complexes (POCNRR΄)NiBr featuring tertiary or secondary amine moieties that exhibit different reactivities as a function of amine substituents R and R΄. For instance, complexes bearing the tertiary amine moieties ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) displayed interesting redox properties and could be converted into their trivalent analogues (POCNR2)NiBr2 when reacted with Br2 or N-bromosuccinimide (NBS). These 17-electron, paramagnetic trivalent complexes adopt a distorted square pyramidal geometry with Br atoms at axial and equatorial positions. DSC and TGA analyses of these compounds revealed them to be thermally stable up to ~170 °C; whereas absorption spectroscopy in solution showed that they undergo thermal decomposition at much lower temperatures to regenerate the monobromo divalent complexes; increased steric bulk of the amine substituents accelerate this decomposition pathway significantly. The NMe2 and N(morpholinyl) analogues of these NiIII species are active catalysts for the Kharasch addition of CX4 to olefins such as styrene, whereas the least thermally stable analogue (POCNEt2)Ni was found to be completely inert for this reaction.
The complexes (POCNRH)NiBr featuring secondary amine moieties allow access to unsymmetrically substituted amine moieties via reaction with alkyl halides. Another important advantage of these complexes lies in the possibility of deprotonation to prepare amide-type POCN complexes. Such attempts at deprotonating the NRH moieties have allowed us to prepare dimeric species featuring bridging amido ligands. The dimeric nature of these complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 and Ph) was established through X-ray diffraction studies that showed different geometries for the Ni2N2 cores as a function of N-substituent: the (PhCH2)N analogue featured a syn orientation of the benzyl substituents and a cyclobutane-like arrangement of Ni and of the nitrogen atoms, whereas the PhN analogue adopted a nearly planar diamond-like arrangement of the Ni and of the nitrogen atoms and an anti orientation of the phenyl substituents. These dimeric species do not dissociate in the presence of alcohols, but they promote the catalytic alcoholysis of acrylonitrile. Interestingly, yields of these reactions are higher with alcohols possessing more acidic O-H moieties, with a catalytic turnover number reaching up to 2000 in the case of m-cresol. These alcoholysis reactions are believed to proceed through heterolytic activation of the alcohol by dimeric species via hydrogen bonding with one or two amido moieties in the dimer.
The dimeric Ni (II) species were found to undergo facile oxidation both electrochemically and in reaction with NBS or Br2. Surprisingly, chemical oxidation led to isolation of new monomeric products in which both the metallic center and the ligand were oxidized. giving a trivalent species featuring an imine-type POCN ligand. Oxidation mechanism was investigated in detail by NMR, UV-vis-NIR, DFT and spectroelectrochemistry.
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Metal catalysed alkylation of carbonyl compounds with formaldehydeLorusso, Patrizia January 2015 (has links)
Formaldehyde is a chemical used widely in the manufacture of building materials. A remarkable example is represented by the Lucite two-step Alpha technology for the large scale production of methyl methacrylate (MMA), the essential building block of all acrylic-based products. Esters and ketones are important intermediates in the manufacture of acrylate esters therefore α-hydroxymethylenation of carbonyl compounds using formaldehyde as a one carbon alkylating agent and subsequent dehydration to the corresponding methylenated derivatives has been explored in the current work. We report a novel catalytic approach for the synthesis of methyl methacrylate (MMA) via one-pot α-methylenation of methyl propanoate (a chemical intermediate of the ALPHA process) with formaldehyde, generated in situ by Ru-catalysed dehydrogenation of methanol. Elucidation of the mechanism involved in the catalytic dehydrogenation of methanol along with the collateral alcohol decarbonylation reaction was gained through a combined experimental and DFT study. The development of an alternative process where anhydrous formaldehyde is produced in situ would provide a simplification over the current second step of the ALPHA technology where the formaldehyde is initially produced as formalin, subsequently dehydrated to afford anhydrous formaldehyde in order to ensure high selectivity to MMA. As an alternative approach, ketones, in particular 3-pentanone and 2-butanone, were targeted as potential substrates in order to overcome some of the problems related to competing reactions that occur at the ester group. Hydroxymethylenation, followed by dehydration and Baeyer-Villager oxidation, possibly catalysed by enzymes to reverse the normal selectivity, leads to the formation of acrylate esters. The catalytic reaction is enabled by a gold carbene hydroxide complex in such a way that the substrate undergoes C-H activation and the nascent metal alkyl acts as a nucleophile towards the electrophilic formaldehyde, supplied in the form of alcoform* (solution of paraformaldehyde in methanol).
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Matériaux composés (polymères électroactif - nanoparticules de métal) et liquides ioniques / Composite materials (electroactive polymer-metal nanoparticles) and ionic liquidsZinovyeva, Veronika 24 September 2010 (has links)
La thèse de doctorat est consacrée aux synthèses de matériaux composites combinant des polymères conducteurs avec des métaux de transition, leur caractérisation par l'utilisation d'un ensemble des méthodes physiques, chimiques et électrochimiques et leur application catalytique. Ces processus ont été réalisés en milieu conventionnel (aqueux et organique) et dans les liquides ioniques à température ambiante. En tant qu’approche de synthèse, nous proposons une méthode simple qui consiste en la réduction chimique de sels inorganiques au moyen de l’oxydation du monomère en milieux variés. La polymérisation du pyrrole en utilisant des sels de Fe(III), Cu(II) et Pd(II) comme oxydants a été réalisée dans une large gamme de conditions de réaction. La cinétique du processus de polymérisation a été étudiée par spectrophotométrie UV-visible et DLS. Les matériaux obtenus ont été caractérisés par les méthodes de voltammétrie cyclique, analyse élémentaire, ICP-AES, AFM, SEM, EDX, TEM, XRD, XPS, XAS, IR. Les propriétés catalytiques et électrocatalytiques des matériaux nanocomposites Pd/polypyrrole ont été analysées pour des réactions du couplage direct hétéroaryle-aryle et l’électrooxidation de l’acide ascorbique. Les procédures alternatives de préparation de polymères conducteurs dans les liquides ioniques, en comparaison avec celles dans les solvents conventionnels, ont été décrites. L’influence des conditions de synthèse sur les propriétés électrochimiques et sur la morphologie des polymères conducteurs a été discutée. L’électrooxidation du ferrocène dans les liquides ioniques a été étudiée en détail, et le modèle du transport diffusionnel dans ces milieux visqueux a été proposé. / The actual PhD thesis is devoted to syntheses of composite materials combining conducting polymers with transition metals, their characterization with the use of a large set of modern physical, chemical and electrochemical methods and initial studies of their catalytic applications. These processes were realized both in conventional (aqueous and organic) media and in room-temperature ionic liquids. As an approach for the chemical synthesis, a simple one-pot non-template method, consisting in the chemical reduction of various inorganic salts by pyrrole monomer in a set of solvents, was applied. Polymerization of pyrrole with the use of Fe(III), Cu(II) and Pd(II) salts as oxidants was carried out in a wide range of reaction conditions. The kinetics of the polymerization process was studied by UV-visible spectroscopy and DLS. The obtained materials were characterized by means of cyclic voltammetry, elemental CHNS analysis, ICP-AES, AFM, SEM, EDX, TEM, XRD, XPS, XAS, IR techniques. Catalytic and electrocatalytic properties of the synthesized Pd/polypyrrole nanocomposites were analyzed for the direct catalytic arylation of heteroaromatics and electrooxidation of ascorbic acid. Alternative ways to conducting polymer preparation in the form of films and powders inside ionic liquids, in comparison to those in conventional media, were described. The influence of the synthesis conditions and of the solvent nature on electrochemical properties and morphology of conducting polymers was discussed. The electrooxidation of ferrocene in ionic liquids was investigated in details, and a model for the diffusional transport in these viscous media was proposed.
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Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior towards Cobalt and Iron Carbonyl Compounds / Ferrocenyl-Alkine und Butadiine: Reaktionsverhalten gegenüber Cobalt- und Eisencarbonyl-verbindungenFilipczyk, Grzegorz Paweł 22 December 2017 (has links) (PDF)
Die vorliegende Dissertation beschreibt die Synthese und Charakterisierung von neuartigen perferrocenylierten, cyclischen Komplexen unter Anwendung der Cobalt-vermittelten Cyclomerisierung in Kombination mit einer C-H-Bindungsaktivierung als auch die Bildung von ferrocenylierten Phosphinoalkinid-Komplexen mit Eisen- und Cobaltcarbonylen. Die elektrochemischen Eigenschaften und die Elektronentransfer-prozesse zwischen den terminalen Ferrocenyleinheiten in den unterschiedlichen cyclischen Verbindungen wurden unter Einbeziehung der Struktur/chemischen Zusammensetzung der Brückenbausteine ermittelt.
Elf perferrocenylierte, cyclische Komplexe wurden mittels [2+2] bzw. [2+2+2] Cyclomerisierung von 1,4-Diferrocenylbutadiin FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) unter Verwendung von Dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2 erhalten. Diese können in drei Gruppen unterteilt werden: (i) Produkte der Cyclodimerisierung mit zusätzlicher Kettenverlängerung, welche Cyclobutadienyl-einheiten als zentrale Brückenbausteine besitzen (3a,b und 4a,b), (ii) Produkte der Cyclodimerisierung mit gleichzeitiger CO-Insertion (6a,b,c und 7), und (iii) Produkte der Cyclotrimerisierung gefolgt von einem Ringschluss durch eine C-H-Bindungsaktivierung (5a,b,c). Die Optimierung der Reaktionsbedingungen wurde zur Ausbeutemaximierung der jeweiligen Verbindungsfamilien durchgeführt.
Ein weiterer Teil dieser Forschungsarbeit bezieht sich auf die verschiedenen Reaktionsmuster von (Ferrocenylethinyl)diphenylphosphan- mit zweikernigen Eisen- bzw. Cobaltcarbonylverbindungen in Form von Dieisennonacarbonyl und Dicobaltoctacarbonyl als Reagenzien. Dabei konnten sechs gemischte Carbonyl- und Ferrocenyl-funktionalisierte Phosphinoacetylid-Komplexe mit Eisen(0) und Cobalt(0) erhalten und charakterisiert werden. / The present PhD study focuses on the synthesis and characterization of novel perferrocenylated cyclic complexes utilizing cobalt - mediated cyclomerization in combination with C–H bond activation as well as formation of ferrocenylated phosphino-alkyne compounds with iron and cobalt carbonyls. Electrochemical properties and electron-transfer processes between terminal ferrocenyl units in the diverse cyclic compounds are explored in relation to the chemical composition of the building blocks connecting them.
Eleven perferrocenylated cyclic compounds were obtained via [2 + 2] and [2 + 2 + 2] cyclomerization of 1,4-diferrocenylbutadiyne FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) by the reaction with dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2. They are subdivided into three groups: (i) products of cyclodimerization with additional chain extension, possessing cyclobutadienyl moieties as a central linkage unit (3a,b and 4a,b), (ii) products of cyclodimerization with consecutive CO insertion (6a,b,c and 7), and (iii) products of cyclotrimerization followed by cycle formation via C–H bond activation (5a,b,c). Optimization of the reaction conditions was made in order to maximize the amount of each group of compounds.
Furthermore, another part of this research work focuses on diverse reaction patterns of (ferrocenylethynyl)diphenylphosphane with diironnonacarbonyl and dicobaltocta-carbonyl. Six mixed carbonyl and ferrocenyl-functionalized phospinoalkynyl compounds of iron(0) and cobalt(0) were obtained and characterized.
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Ferrocenyl-Alkynes and Butadiynes: Reaction Behavior towards Cobalt and Iron Carbonyl CompoundsFilipczyk, Grzegorz Paweł 04 December 2017 (has links)
Die vorliegende Dissertation beschreibt die Synthese und Charakterisierung von neuartigen perferrocenylierten, cyclischen Komplexen unter Anwendung der Cobalt-vermittelten Cyclomerisierung in Kombination mit einer C-H-Bindungsaktivierung als auch die Bildung von ferrocenylierten Phosphinoalkinid-Komplexen mit Eisen- und Cobaltcarbonylen. Die elektrochemischen Eigenschaften und die Elektronentransfer-prozesse zwischen den terminalen Ferrocenyleinheiten in den unterschiedlichen cyclischen Verbindungen wurden unter Einbeziehung der Struktur/chemischen Zusammensetzung der Brückenbausteine ermittelt.
Elf perferrocenylierte, cyclische Komplexe wurden mittels [2+2] bzw. [2+2+2] Cyclomerisierung von 1,4-Diferrocenylbutadiin FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) unter Verwendung von Dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2 erhalten. Diese können in drei Gruppen unterteilt werden: (i) Produkte der Cyclodimerisierung mit zusätzlicher Kettenverlängerung, welche Cyclobutadienyl-einheiten als zentrale Brückenbausteine besitzen (3a,b und 4a,b), (ii) Produkte der Cyclodimerisierung mit gleichzeitiger CO-Insertion (6a,b,c und 7), und (iii) Produkte der Cyclotrimerisierung gefolgt von einem Ringschluss durch eine C-H-Bindungsaktivierung (5a,b,c). Die Optimierung der Reaktionsbedingungen wurde zur Ausbeutemaximierung der jeweiligen Verbindungsfamilien durchgeführt.
Ein weiterer Teil dieser Forschungsarbeit bezieht sich auf die verschiedenen Reaktionsmuster von (Ferrocenylethinyl)diphenylphosphan- mit zweikernigen Eisen- bzw. Cobaltcarbonylverbindungen in Form von Dieisennonacarbonyl und Dicobaltoctacarbonyl als Reagenzien. Dabei konnten sechs gemischte Carbonyl- und Ferrocenyl-funktionalisierte Phosphinoacetylid-Komplexe mit Eisen(0) und Cobalt(0) erhalten und charakterisiert werden.:Table of contents
Bibliografische Beschreibung und Referat iii
Abstract iv
Ort und Zeitraum der Durchführung v
Widmung vi
Präambel vii
List of Abbreviations xii
CHAPTER A Introduction 15
References 16
CHAPTER B State of Knowledge 19
1 (Spectro)electrochemical studies of mixed-valent transition metal complexes. Theoretical background 19
1.1 Mixed-valent compounds – classification 20
1.2 Spectroelectrochemistry 21
1.3 Electrochemistry 25
2 (Di)ferrocenylalkynes – synthesis and reactions 28
2.1 1,4-Diferrocenylbutadiyne 29
2.2 Other (poly)ferrocenyl substituted alkyne derivatives 35
3 Dicarbonylcyclopentadienylcobalt – [2+2] and [2+2+2] cyclo-addition reactions 37
3.1 [2+2] and [2+2+2] cycloaddition – cyclobutadiene, cyclopentadienone, benzene and pyridine based systems 38
3.2 Mechanism of [2+2] and [2+2+2] cycloaddition/cyclization and [2+2] cycloaddition/cyclization with CO insertion mediated by CoCp(CO)2 40
4 Chelation-assisted C–H bond activation mediated by cobalt species 42
5 Phosphinoalkynes and their reaction with iron and cobalt carbonyls 44
5.1 Mechanism of the P–C(sp) bond cleavage in phosphinoalkynes 48
6 Complexes setup by (ferrocenylethynyl)diphenylphosphane 50
References 56
CHAPTER C Multiferrocenyl Cobalt-Based Sandwich Compounds 64
1 Introduction 64
2 Results and Discussion 65
2.1 Synthesis and Characterization 65
2.2 Solid-State Structures 71
2.3 Electrochemistry 73
2.4 Spectroelectrochemistry 76
3 Experimental Section 79
3.1 Instrumentation 79
3.2 General Conditions 81
3.3 Reagents 81
3.4 General Procedure - Reaction of 1 with 2 81
3.4.1 Compound 3a 82
3.4.2 Compound 3b 82
3.4.3 Compound 4b 83
3.4.4 Compound 5c 83
3.4.5 Compound 6a 84
3.4.6 Compound 6b 84
3.4.7 Compound 6c 85
3.4.8 Compound 7 85
4 Supporting information 86
5 References 86
CHAPTER D Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures 91
1 Introduction 91
2 Results and Discussion 92
3 Experimental Section (Supporting information) 98
3.1 General Information 98
3.2 Starting Materials 98
3.3 Synthesis of 3a and 3b from 2 99
3.3.1 Complex 3a: 99
3.3.2 Complex 3b: 100
3.4 Synthesis of 9a and 9b from 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 101
3.4.1 Synthesis of 1-Bromo-2-Ferrocenylethynyl Benzene (7) 101
3.4.2 Synthesis of 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 102
3.4.3 Synthesis of 9a and 9b from 8 103
3.5 Synthesis of 3a and 3b from 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.1 Synthesis of 1,3,5-Trichloro-2,4,6-Triethynylferrocenyl Benzene (12) 105
3.5.2 Synthesis of 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.3 Synthesis of 3a and 3b from 4 106
4 Supporting information 107
4.1 Spectroelectrochemistry of 3a,b 107
4.2 Conversion of Isomer 9a to 9b – Electrochemical and Chemical oxidation 109
4.3 Chemical oxidation experiment 110
5 References 111
CHAPTER E Coordination Behavior of (Ferrocenylethynyl)diphenyl-phosphane Towards Binuclear Iron and Cobalt Carbonyls 114
1 Introduction 114
2 Results and Discussion 115
3 Experimental Section 126
3.1 Instrumentation 126
3.2 General 128
3.3 Reagents 128
3.4 Synthesis of 4 128
3.5 Synthesis of 4, 5 and 6 129
3.6 Synthesis of 6 by reacting 4 with 2 131
3.7 Synthesis of 7 and 8 131
3.8 Synthesis of 8 from 1 with 3 132
3.9 Synthesis of 9 in the reaction of 7 with 2 133
3.10 Synthesis of 9 in the reaction of 4 with 3 133
4 Electronic Supplementary Material (Supporting information) 134
5 References 134
CHAPTER F Summary 139
1 Conclusions of Chapter C (Appendix A) 139
2 Conclusions of Chapter D (Appendix B) 141
3 Conclusions of Chapter E (Appendix C) 142
Appendix 145
1 Appendix D (Chapter C) 145
2 Appendix E (Chapter D) 146
3 Appendix F (Chapter E) 147
Curriculum Vitae 150
Publications 152
Acknowledgements 154
Selbstständigkeitserklärung 155 / The present PhD study focuses on the synthesis and characterization of novel perferrocenylated cyclic complexes utilizing cobalt - mediated cyclomerization in combination with C–H bond activation as well as formation of ferrocenylated phosphino-alkyne compounds with iron and cobalt carbonyls. Electrochemical properties and electron-transfer processes between terminal ferrocenyl units in the diverse cyclic compounds are explored in relation to the chemical composition of the building blocks connecting them.
Eleven perferrocenylated cyclic compounds were obtained via [2 + 2] and [2 + 2 + 2] cyclomerization of 1,4-diferrocenylbutadiyne FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) by the reaction with dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2. They are subdivided into three groups: (i) products of cyclodimerization with additional chain extension, possessing cyclobutadienyl moieties as a central linkage unit (3a,b and 4a,b), (ii) products of cyclodimerization with consecutive CO insertion (6a,b,c and 7), and (iii) products of cyclotrimerization followed by cycle formation via C–H bond activation (5a,b,c). Optimization of the reaction conditions was made in order to maximize the amount of each group of compounds.
Furthermore, another part of this research work focuses on diverse reaction patterns of (ferrocenylethynyl)diphenylphosphane with diironnonacarbonyl and dicobaltocta-carbonyl. Six mixed carbonyl and ferrocenyl-functionalized phospinoalkynyl compounds of iron(0) and cobalt(0) were obtained and characterized.:Table of contents
Bibliografische Beschreibung und Referat iii
Abstract iv
Ort und Zeitraum der Durchführung v
Widmung vi
Präambel vii
List of Abbreviations xii
CHAPTER A Introduction 15
References 16
CHAPTER B State of Knowledge 19
1 (Spectro)electrochemical studies of mixed-valent transition metal complexes. Theoretical background 19
1.1 Mixed-valent compounds – classification 20
1.2 Spectroelectrochemistry 21
1.3 Electrochemistry 25
2 (Di)ferrocenylalkynes – synthesis and reactions 28
2.1 1,4-Diferrocenylbutadiyne 29
2.2 Other (poly)ferrocenyl substituted alkyne derivatives 35
3 Dicarbonylcyclopentadienylcobalt – [2+2] and [2+2+2] cyclo-addition reactions 37
3.1 [2+2] and [2+2+2] cycloaddition – cyclobutadiene, cyclopentadienone, benzene and pyridine based systems 38
3.2 Mechanism of [2+2] and [2+2+2] cycloaddition/cyclization and [2+2] cycloaddition/cyclization with CO insertion mediated by CoCp(CO)2 40
4 Chelation-assisted C–H bond activation mediated by cobalt species 42
5 Phosphinoalkynes and their reaction with iron and cobalt carbonyls 44
5.1 Mechanism of the P–C(sp) bond cleavage in phosphinoalkynes 48
6 Complexes setup by (ferrocenylethynyl)diphenylphosphane 50
References 56
CHAPTER C Multiferrocenyl Cobalt-Based Sandwich Compounds 64
1 Introduction 64
2 Results and Discussion 65
2.1 Synthesis and Characterization 65
2.2 Solid-State Structures 71
2.3 Electrochemistry 73
2.4 Spectroelectrochemistry 76
3 Experimental Section 79
3.1 Instrumentation 79
3.2 General Conditions 81
3.3 Reagents 81
3.4 General Procedure - Reaction of 1 with 2 81
3.4.1 Compound 3a 82
3.4.2 Compound 3b 82
3.4.3 Compound 4b 83
3.4.4 Compound 5c 83
3.4.5 Compound 6a 84
3.4.6 Compound 6b 84
3.4.7 Compound 6c 85
3.4.8 Compound 7 85
4 Supporting information 86
5 References 86
CHAPTER D Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures 91
1 Introduction 91
2 Results and Discussion 92
3 Experimental Section (Supporting information) 98
3.1 General Information 98
3.2 Starting Materials 98
3.3 Synthesis of 3a and 3b from 2 99
3.3.1 Complex 3a: 99
3.3.2 Complex 3b: 100
3.4 Synthesis of 9a and 9b from 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 101
3.4.1 Synthesis of 1-Bromo-2-Ferrocenylethynyl Benzene (7) 101
3.4.2 Synthesis of 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 102
3.4.3 Synthesis of 9a and 9b from 8 103
3.5 Synthesis of 3a and 3b from 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.1 Synthesis of 1,3,5-Trichloro-2,4,6-Triethynylferrocenyl Benzene (12) 105
3.5.2 Synthesis of 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105
3.5.3 Synthesis of 3a and 3b from 4 106
4 Supporting information 107
4.1 Spectroelectrochemistry of 3a,b 107
4.2 Conversion of Isomer 9a to 9b – Electrochemical and Chemical oxidation 109
4.3 Chemical oxidation experiment 110
5 References 111
CHAPTER E Coordination Behavior of (Ferrocenylethynyl)diphenyl-phosphane Towards Binuclear Iron and Cobalt Carbonyls 114
1 Introduction 114
2 Results and Discussion 115
3 Experimental Section 126
3.1 Instrumentation 126
3.2 General 128
3.3 Reagents 128
3.4 Synthesis of 4 128
3.5 Synthesis of 4, 5 and 6 129
3.6 Synthesis of 6 by reacting 4 with 2 131
3.7 Synthesis of 7 and 8 131
3.8 Synthesis of 8 from 1 with 3 132
3.9 Synthesis of 9 in the reaction of 7 with 2 133
3.10 Synthesis of 9 in the reaction of 4 with 3 133
4 Electronic Supplementary Material (Supporting information) 134
5 References 134
CHAPTER F Summary 139
1 Conclusions of Chapter C (Appendix A) 139
2 Conclusions of Chapter D (Appendix B) 141
3 Conclusions of Chapter E (Appendix C) 142
Appendix 145
1 Appendix D (Chapter C) 145
2 Appendix E (Chapter D) 146
3 Appendix F (Chapter E) 147
Curriculum Vitae 150
Publications 152
Acknowledgements 154
Selbstständigkeitserklärung 155
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POCN-type Pincer Complexes of NiII and NiIII : synthesis, reactivities, catalytic activities and physical propertiesSpasyuk, Denis M. 08 1900 (has links)
No description available.
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Selektive Halogenierungen unter Phasentransferbedingungen: Mechanistische Untersuchungen und Synthetische AnwendungenLauenstein, Oliver 27 June 2001 (has links)
No description available.
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Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexesBoyd, Ramon Cornell 23 January 2007
Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization.
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