In this study a bidentate ligand containing two ferrocenyl moieties, N,N&#039 / -bis(ferrocenylmethylene)ethylenediamine, was prepared by condensation reaction of ferrocenecarboxyaldehyde and ethylenediamine on refluxing in benzene. The molecule was identified by IR, Raman, UV-VIS, 1H-, 13C-NMR spectroscopies. Then, this bidentate ligand was reacted with pentacarbonylbis-(trimethyl)silylethyne)tungsten(0). The ligand substitution reaction in dichloromethane yielded the new complex, tetracarbonyl [N,N&#039 / -bis(ferrocenylmethylene)ethylenediamine]tungsten(0) (W(CO)4(BFEDA)). This new complex was isolated from the reaction solution in the form of orange crystals and fully characterized by elemental analysis, IR, UV-VIS, MS, 1H- and 13C-NMR spectroscopies. As a bidentate ligand, [N,N&#039 / -bis(ferrocenylmethylene)ethylenediamine] binds the metal atom in the two cis positions in the pseudooctahedral geometry of the tungsten-complex. Electrochemistry of the tetracarbonyl [N,N&#039 / -bis(ferrocenylmethylene)ethylenediamine]tungsten(0) was studied by cyclic voltammetry, and controlled potential electrolysis combined with the UV-VIS spectroscopy. One irreversible oxidation and three reversible oxidations were observed in the cyclic voltammogram. One of these reversible and the irreversible oxidations are attributed to tungsten and the other two reversible oxidations to iron centers. It is found that the two ferrocene groups started communication with each other after formation of tungsten-complex. N,N&#039 / -bis(ferrocenylmethylene)ethylenediamine was also reacted with photogenerated pentacarbonyl(tetrahydrofuran)tungsten(0) complex and the pentacarbonyl [N,N&#039 / -bis(ferrocenylmethylene)ethylenediamine]tungsten(0) (W(CO)5(BFEDA)) as an intermediate on the route to the tetracarbonyl[N,N&#039 / -bis(ferrocenylmethylene)ethylenediamine]tungsten(0) was isolated from the reaction medium in the form of red crystals and fully characterized by, IR, 1H- and 13C-NMR spectroscopies. The conversion of W(CO)5(BFEDA) to the W(CO)4(BFEDA) in dichloromethane by a ring closure mechanism was observed by IR spectroscopy.

SYNTHESIS OF FERROCENYLIDENE CYCLOPENTENEDIONES K&ouml / kt&uuml / rk, Mustafa M.S., Department of Chemistry Supervisor: Assoc. Prof. Dr. Metin Zora August 2005, 83 pages 2-Arylidine-4-cyclopentene-1,3-diones are known to be antitumor agents. Incorporation of the essential structures of such compounds with a ferrocene moiety instead of an aryl group could provide subtances with enhanced antitumor activities since some ferrocene derivatives have already proved to be active against a number of tumors. Thus, we have investigated the squarate-based synthesis of 2-ferrocenylidene-4-cyclopentene-1,3-diones. Upon thermolysis, 4-hydroxy-4-ferrocenylethynyl-2-cyclobutenones, prepared from 3-cyclobutene-1,2-diones and lithioethynylferrocene, produced exclusively 2-ferrocenylidene-4-cyclopentene-1,3-diones. In some cases, ferrocenyl quinone derivatives are obtained in very minor amounts. Moreover, the heating of a mixture of 4-ferrocenylethynyl-4-hydroxy-2-cyclobutenones and silica gel in oven at 120 oC without using any solvent provided the same type of products. More importantly, the stirring of a solution of 4-ferrocenylethynyl-4-hydroxy-2-cyclobutenone (37A-C) derivatives in ethyl acetate at the room temperature yielded the same type products, as well. It appears that 4-hydroxy-4-ferrocenylethynyl-2-cyclobutenones are more reactive than corresponding phenyl analogs. For the formation of ferrocenyl-substituted cyclopentenediones, a mechanism involving first electrocyclic ring opening of ferrocenylethynyl-substituted cyclobutenones to corresponding ketene intermediate and then ring closure, has been proposed. The exclusive formation of cyclopentenediones is attributed to the radical stabilizing ability of the ferrocenyl moiety during the course of the reaction.

ABSTRACT SYNTHESIS OF FERROCENYL QUINONES AND POLYQUINANES Eralp, Tug&ccedil / e 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.

In this study, a bidentate ligand, 6-ferrocenyl-2,2&#039 / -bipyridine, was prepared by the reaction of lithiated ferrocene with bipyridine. The ligand was identified by 1H, 13C- NMR and HMQC and UV-Vis spectroscopies. Then, bidentate molecule was reacted with pentacarbonylbis-(trimethylsilylethyne)tungsten(0). The ligand substitution reaction in CH2Cl2 yielded the new complex, tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0). The isolated and purified complex was fully characterized by elemental analysis, IR, UV-Vis, MS, 1H and 13C- NMR spectroscopies. Tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)chromium(0) was also formed by ligand substitution reaction of 6-ferrocenyl-2,2&#039 / -bipyridine with pentacarbonyl(THF)chromium(0) which was prepared by photolytic substitution of CO from hexacarbonyl chromium(0) in THF. However, tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)chromium(0) could not be isolated by column chromatography. Electrochemistry of 6-ferrocenyl-2,2&#039 / -bipyridine and tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0) was studied by cyclic voltammetry and controlled potential electrolysis combined with UV-Vis. The ligand exhibits a reversible reduction and a reversible oxidation belonging to bipyridine and ferrocene moieties, respectively. One reversible reduction, two irreversible oxidation and a reversible oxidation were observed for tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0). The reversible reduction was attributed to bipyridine whereas two irreversible oxidations were assigned to tungsten centers and reversible oxidation to iron center.

Thesis (B.S.) Magna Cum Laude--Butler University, 2007. / Includes bibliographical references (leaves 26-27).

CRUZ, M. G. A. Catalisadores baseados em Fe-C mesoporosos para síntese de Fischer-Tropsch. 2017. 97 f. Tese (Doutorado em Engenharia Química)–Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2017. / Submitted by Marlene Sousa (mmarlene@ufc.br) on 2017-09-06T14:51:50Z No. of bitstreams: 1 2017_tese_mgacruz.pdf: 4026668 bytes, checksum: 3c2516a4d0b0ba6bcae042831861b0a6 (MD5) / Approved for entry into archive by Marlene Sousa (mmarlene@ufc.br) on 2017-09-06T15:38:26Z (GMT) No. of bitstreams: 1 2017_tese_mgacruz.pdf: 4026668 bytes, checksum: 3c2516a4d0b0ba6bcae042831861b0a6 (MD5) / Made available in DSpace on 2017-09-06T15:38:26Z (GMT). No. of bitstreams: 1 2017_tese_mgacruz.pdf: 4026668 bytes, checksum: 3c2516a4d0b0ba6bcae042831861b0a6 (MD5) Previous issue date: 2017-02-10 / This work deals with the influence of preparation methods of Fe - containing carbon catalysts for Fischer - Tropsch Synthesis (SFT). For these purposes, two series of solids were prepared. The first series was the Fe - based catalysts supported o n polystyrene mesoporous carbon pretreated at dif ferent calcination temperatures. The second series of materials was the solids prepared by distinct preparation methods. All solids were characterized by X - ray diffract ion (XRD) , Raman spectroscopy, s canning and t ransmission electron microcopies (SEM and TEM), textural properties, elemental composition by X - ray dispersive spectroscopy (EDS), temperature programmed reduction (TPR) and X - ray photoelectron spectroscopy (XPS). It was shown that the preexistent carbides phases obtained in the Fe - containing polymeric mesoporous carbons upon using elevated temperatures of calcinations resulted in a solid with good textural and structural properties. However, these materials were not comp letely reoxidized during the SFT reaction while the formation of carbides through the polymeric carbon reaction with magnetite and  or metallic iron resulted in highly active catalysts for SFT . The second series of materials applied copolymer assisted co - p recipitation of iron precursor (CP) , chemical modification of ferrocene (CM) , sol - gel (SG) and wetness impregnation of iron on polymeric carbon (IM) methods . SG method solid resulted in a conversion of syngas up to 56% and productivity of 34 mg hydrocarbon .g cat - 1 .h - 1 at 240 o C and 20 atm. IM gave a Fe/C based catalyst with the highest exposure of active sites, including surface Fe 3+ and Fe 2+ redox sites with great properties in SFT . CM route enabled the formation of hematite and maghemite nanoparticles on ca rbon, which were reduced in situ to magnetite and iron carbide s, the latt er being the most active for the water - gas - shift reaction (RWGS) reaction. It was found that copolymer assisted CP facilitate d the production of large crystals of magnetite, which suf fered sintering and coking in SFT . Among these methods, SG proved to have superior performance due to the good dispersion of Fe, stable magnetite as well as iron carbide and Fe - doped nitrogen carbon phases production. / A proposta deste trabalho é estudar a influência do método de preparação de catalis adores contendo Fe - carbono para a reação de Fischer - Tropsch (SFT). Para este fim, duas séries de sólidos foram preparadas. A primeira série foi composta de Fe contendo carbono pré - tratados em diferentes temperaturas de calcinação . A segunda série de materi ais é composta por sólidos obtidos por distintos métodos de preparação. Todos os materiais foram caracterizados por difração de raios - X (DRX), e spectroscopia Raman, m icroscopias eletrônicas de varredura e transmissão (SEM e TEM), propriedades texturais, co mposição elementar por espectroscopia de energia dispersiva de raios - X (EDS), redução termoprogramada (TPR) e espectros copia fotoeletrônica de raios - X (XPS). Os resultados revelaram que os carbetos formados nos sólidos de Fe impregnados em carbono poliméri co mesoporoso resultaram em boas propriedades texturais e estruturais. No entanto, estes materiais não foram completamente oxidados durante a reação de SFT, enquanto qu e a formação de carbetos oriundos da reação de magnetita e  ou ferro metálico resultaram em catalisadore s ativos para SFT. A segunda série de materiais aplicou os métodos de co - precipitação assistida do copolímero com o precursor de ferro (CP), modificação química do ferroceno (CM), sol - gel (SG) e impregnação de ferro sobre o carbono poliméric o (IM). O método de preparação SG resultou em uma conversão do gás de síntese de 56% e produtividade de 34 mg hidrocarboneto .g cat - 1 .h - 1 a 240 o C e 20 atm. O método IM gerou um catalisador de Fe/C com sítios ativos bastante expostos, incluindo os sítios redo x Fe 3+ e Fe 2+ superficiais que possuem excelentes propriedades em SFT. A rota CM possibilitou a formação de nanopartículas de hematita e maguemita sobre o carbono, os quais foram reduzidos in situ à magnetita e carbeto de ferro, sendo a última espécie alt amente ativa na reação reversa de shift (RWGS) . A síntese de co - precipitação assistida do copolímero, CP, facilitou a formação de grandes cristais de magnetita, que sofreram sinterização e coqueamento na SFT. Dentre esses métodos, o método SG mostrou desem penho superior aos demais, devido à boa dispersão de Fe bem como à produção das fases magnetita estável e Fe contendo carbono dopado com nitrogênio.

Title: Phosphinoferrocene ligands with polar amide substituents Author: Hana Charvátová Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Abstract: This thesis is focused on phosphino-urea ferrocene ligands that are still rather neglected in the literature. It describes the synthesis of novel polar amides and hydrazides of 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) with or without ethylene linker bearing various urea and guanidine terminal functional groups. Urea and guanidine derivatives with ethylene bridge can be prepared from Hdpf and appropriate amine with amidation agents. Phosphine ureas without the linker are accessible from reactions of primary amide of Hdpf with suitable acylation agents while analogical guanidine is obtained from guanylation of amide-amine generated from Hdpf acylbenzotriazole and ethylenediamine. Reaction of the acylbenzotriazole with free guanidine leads to [1-(diphenylphosphino)ferrocenecarbonyl]guanidine hydrochloride. These ferrocene ligands were used to prepare four types of palladium(II) complexes, viz. where L denotes the newly synthesized ligands and LNC is 2- [(dimethylamino)methyl]phenyl-C,N auxiliary chelating ligand. Catalytic efficiency of complexes with ethylene bridge was tested on reactions of aromatic...

This thesis deals with the copper-catalyzed substitution of allylic substrates. In the first part of this thesis, the synthesis of a series of metallocenethiolates is described. The thiolates were examined as ligands in the enantioselective copper(I)-catalyzed γ-substitution of allylic acetates. The second part describes a study on copper-catalyzed α-substitution of enantiomerically pure secondary allylic esters. It was observed that the degree of chirality transfer is strongly dependent on the reaction temperature. The loss of chiral information is consistent with an equilibration of the allylCu(III) intermediates prior to product formation, which is essential in order to realize a copper-catalyzed dynamic kinetic asymmetric transformation process. The third part describes a study on copper-catalyzed stereoselective α-substitution of enantiopure acyclic allylic esters. This method, when combined, with ruthenium and enzyme catalyzed dynamic kinetic resolution of allylic alcohols, provides a straightforward route to pharmaceutically important α-methyl carboxylic acids. The fourth part is a mechanistic study on the reaction of perfluoroallyl iodide with organocuprates. Experimental studies as well as theoretical calculations were used to explain the contrasting reactivity of perfluoroallyl iodide vs. allyl iodide in cuprate allylation reactions. In the fifth part, the development of a practical and useful method for the preparation of pentasubstituted acylferrocenes is presented.

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No description available.