The Structure and Chemistry of Ferrocene. VI. Mechanism of the Arylation Reaction

Synthesis, electrochemical and spectroelectrochemical studies of metal-free 2,9,16,23-tetraferrocenylphthalocyanine

“…2, 2. Preparatian of 1 -( 3, 4-frcy arnp luny I ) ferrocene ( 4 ) Using a method previously described for the preparation of phenylferrocene [28], ferricenium chloride (2) reacted with 4-diazoniumphthalonitrile bisulfate (3) [29] to give 1-(3,4-dicyanophenylXerrocene (4). Compound (4) was thus prepared by dissolving ferrocene (3.3 g, 0.017 mol) in anhydrous diethyl ether (30 mL), followed by oxidation by the addition of ferric chloride/ diethyl ether.…”

“…The first fraction, ferrocene, was followed by a blood-red fraction which gave 3.1 g of a mixture of 4 and phthalonitrile. The solvent system was then changed to acetonitrile:benzene (1 : 10) yielding a dark-red, fraction which likely contained a mixture of a disubstituted ferrocene and 3,4,3',4'-tetraryanobiphenyl [28]. The first fraction was further purified on a classical silica-gel column using ethyl acetate:petroleum ether (30-60"C) (25:100) as eluant yielding 4 (2.4…”

Reactions of Ferrocenium Hexafluorophosphate with P−OR Nucleophiles Give Ring C−H Functionalization or Ring Replacement Products Depending on the Phosphorus Reagent

“…It has been known for almost 70 years that ferrocenium salts can undergo radical substitution reactions. These include alkylation, [1] cyanalkylation, [2,3] arylation, [2,[4][5][6][7] acylation, [8] and azolation. [9] However, the mechanistic details of the CÀ H bond breaking have never been studied for such processes; therefore, the type of the leaving group (H * or H + ) remains unclear.…”

Síntese de poli(1,1'-ferrocenilenovinileno) via acoplamento de McMurry

“…Em reações de Friedel-Crafts, por exemplo, sua reatividade pode alcançar 10 6 vezes a reatividade do benzeno [7] . Assim, inúmeros derivados podem ser preparados a partir do ferroceno, de modo a construir estruturas diversas com o emprego deste metaloceno (Figura 1) [8][9][10][11][12][13] . Entre as diversas classes de polímeros conjugados, a família dos poli(arilenovinileno)s (PAVs) [14] (Figura 2), cujo representante mais conhecido é o poli(p-fenilenovinileno) (1,1'-ferrocenilenovinileno Resumo: Com base nas grandes modificações das propriedades de materiais poliméricos resultantes da inclusão de unidades organometálicas, descrevem-se neste trabalho a síntese e a caracterização de um polímero organometálico conjugado com estrutura semelhante à de poli(p-fenilenovinileno) (PPV), o qual apresenta grupos 1,1'-ferrocenileno no lugar de 1,4-fenileno em sua cadeia principal.…”