Archives for Chemistry Experiments of Vinylferrocene

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Synthesis and properties of ferrocenylalkyl derivatives of indazole

Ferrocenylmethylation and alpha-ferrocenylethylation of indazole were carried out for the first time. Both reactions afforded two isomers, which were characterized by physical and physicochemical methods, among them by X-ray diffraction analysis. 1-(alpha-Ferrocenylethyl)indazole is thermally more stable than the 2-substituted isomer. Both isomers serve as ferrocenylalkylating agents with respect to s-triazole.

Synthesis and properties of ferrocenylalkyl derivatives of indazole

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ferrocenyl bisoxazoline as an efficient non-phosphorus ligand for palladium-catalyzed copper-free Sonogashira reaction in aqueous solution

Pd(OAc)2-catalyzed Sonogashira coupling reactions of alkynes and a variety of aryl halides with 1,3-bis(5-ferrocenylisoxazoline-3-yl)benzene as an efficient non-phosphorus ligand under copper-free conditions are presented. The main advantages over previous methodologies include low catalyst loading (0.2 mol% Pd(OAc)2 and 0.4 mol% ferrocenyl bisoxazoline ligand are sufficient for these coupling reactions), less problematic reaction medium (water?dimethylformamide) and more convenient operation (no requirement for nitrogen protection).

Ferrocenyl bisoxazoline as an efficient non-phosphorus ligand for palladium-catalyzed copper-free Sonogashira reaction in aqueous solution

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Isophorone-based organometallic chromophores: Synthesis, characterization and investigation of electro-optical properties

A series of hybrid donor?acceptor complexes with a ferrocene moiety and isophorone derivatives were synthesized. Data from 1H NMR, 13C NMR, Fourier transform infrared, atomic absorption and mass spectroscopies and CHN analysis supported the predicted structure of the products. A comparative investigation was performed using UV?visible, cyclic voltammetry and fluorescence measurements. Density functional theory was used to optimize the chromophore structure and calculation of highest occupied and lowest unoccupied molecular orbital energy levels. The ferrocene/isophorone hybrids show useful properties for further development and studies as electro-optic materials.

Isophorone-based organometallic chromophores: Synthesis, characterization and investigation of electro-optical properties

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Internal adduct formation of active intramolecular C4-bridged frustrated phosphane/borane Lewis pairs

The tetramethylene-bridged PMes2/B(C6F 5)2 frustrated Lewis pair (FLP) 8 was prepared by hydroboration of Mes2P-(CH2)2CH=CH2 with HB(C6F5)2. It is an active FLP that splits dihydrogen under mild conditions and, consequently, serves as a metal-free hydrogenation catalyst for a variety of substrates. It also reacts typically with terminal acetylenes. The C4-bridged FLP 23 was prepared by HB(C6F5)2 hydroboration of 1- dimesitylphosphino-2-vinylferrocene. It represents a rare example of a FLP where the equilibrium between the open form and the closed internal P/B adduct form is experimentally observable. It also shows a variety of typical FLP reactions, including dihydrogen splitting. The FLPs 8 and 23 (open form) and many precursors and products were characterized by X-ray diffraction.

Internal adduct formation of active intramolecular C4-bridged frustrated phosphane/borane Lewis pairs

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Direct Access to Chiral Secondary Amides by Copper-Catalyzed Borylative Carboxamidation of Vinylarenes with Isocyanates

A Cu-catalyzed borylative carboxamidation reaction has been developed using vinylarenes and isocyanates. Alkynes, branched 1,3-dienes, and bicyclic alkenes were also found to be competent coupling partners. Using a chiral phosphanamine ligand, an enantioselective variant of this transformation was developed, affording a set of alpha-chiral amides with unprecedented levels of enantioselectivity. The synthetic utility of the method was demonstrated through a series of representative stereoretentive postcatalytic derivatizations.

Direct Access to Chiral Secondary Amides by Copper-Catalyzed Borylative Carboxamidation of Vinylarenes with Isocyanates

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Epoxy-encapsulated ceramic superconductor microelectrodes

A procedure is outlined for fabricating well-behaved microelectrodes from ceramic pellets of YBa2Cu3O7 and Bi2Sr2CaCu2O8 which involves systematic polishing of an epoxy-encapsulated superconductor chip, under Et4NClO4/acetonitrile solution, to a potentiometric end point. Voltammetry of the resulting microelectrodes in acetonitrile is illustrated and compared to that arising from alternative superconductor electrode geometries. The microelectrodes have active electrode surface areas ranging from 2 ¡Á 10-6 to 3 ¡Á 10-4 cm2, as characterized electrochemically and microscopically. The results are significant steps toward developing the methodology necessary to study the electrochemical response of high temperature superconductor phases at temperatures below their superconductor critical temperature.

Epoxy-encapsulated ceramic superconductor microelectrodes

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

Archives for Chemistry Experiments of Vinylferrocene

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Ring-strain effects on the oxidation potential of enediynes and enediyne complexes.

The metal-enediyne complexes [(eta 5-C5H5)Fe[eta 5-1,2-C5H3C identical to C(CH2)nC identical to]] (4, n = 4; 5, n = 5) and [(eta 5-C5H5)-Fe[eta 5-1,2-C5H3(C identical to C Me)2]] (6) were prepared from 1,2-diethynylferrocene (3). Complexes 4 and 5 were characterized in the solid state by X-ray crystallographic analysis. The structures of 4 and 6 were determined by computation using ab initio methods. A correlation was observed between ring-strain and increased ease of electrochemical oxidation along the series 6 (+0.164 V) to 5(+0.152 V) to 4 (+0.123 V). A similar trend in ionization potentials was identified in both the gas phase and in solution by computational methods.

Ring-strain effects on the oxidation potential of enediynes and enediyne complexes.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Synthesis of new star-like triply ferrocenylated compounds

New ferrocenyl-subtituted compounds containing two different central cores (isocyanurate and 1,3,5-phenylene) and extended by two kinds of branches bearing both vinyl ferrocenyl (1 and 3) and cross-conjugated ferrocenyl-chalcone (2, 4 and 5) as endgroups have been synthetized and characterized both spectroscopically and electrochemically. These molecules have been synthesized in order to investigate the electronic properties imparted by both types of branches when they are connected to the central core. For all compounds, electrochemical studies have showed a simultaneous oxidation of all ferrocene units present in each compound. For all of them, except for compound 2, a chemically reversible oxidation wave on the voltammograms has been observed. In contrast, for compound 2, a chemically irreversible oxidation wave is obtained. Moreover, the vinyl ferrocenyl derivatives have presented a lower redox peak potential with respect to ferrocene standard compound, and the ferrocenyl-chalcone bearing derivatives, in accordance with a change in the electron releasing capability of these endgroups, have been oxidized at a higher potential. Bathochromic shifts of the active transitions in Uv-Vis region have been observed, which are associated to the presence of carbonyl groups in those molecular structures containing it. These results are in agreement with theoretically calculated transition energies, which have been obtained for compounds 1 and 2 using Time Dependent Density Functional Theory (TD-DFT).

Synthesis of new star-like triply ferrocenylated compounds

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Difluoromethylcarbene for iron-catalyzed cyclopropanation

Difluoroethylsulfonium salt, Ph2S+CH2CF2H OTf?, was developed into a convenient difluoromethylcarbene reagent for the iron-catalyzed cyclopropanation of terminal olefins, giving various difluoromethyl-cyclopropanes with excellent diastereoselectivities and in high yields.

Difluoromethylcarbene for iron-catalyzed cyclopropanation

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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New synthesis of acylferrocene by hydroiminoacylation of the terminal olefin with ferrocenecarboxaldimine and application to polymer-supported acylferrocene

Acylferrocenes were synthesized by hydroiminoacylation of the omega-olefins 1-pentene (3a), vinylferrocene (3b) and but-3-enylferrocene (3c), with the ferrocenecarboxaldimine 2, prepared from ferrocenecarboxaldehyde (1) and 2-amino-3-picoline, under the action of Wilkinson’s catalysts, followed by hydrolysis of the corresponding ketimines (5a, 5b and 5c).This hydroiminoacylation was used to incorporate the ferrocenyl group into phenyl-terminated poly-butadiene (PTPB, consisting of 27percent vinyl and 73percent internal olefin group). 74percent hydroacylation of the vinyl group in 7 wasaccomplished in the first catalytic reaction and in 10 the second hydroacylation completed the conversion of the vinyl group into acylferrocene.

New synthesis of acylferrocene by hydroiminoacylation of the terminal olefin with ferrocenecarboxaldimine and application to polymer-supported acylferrocene

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion