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The direct high-yield synthesis without solvent and catalyst, under mild conditions, of eleven novel mono substituted ferrocenylmethyl ethers and amine derivatives from ferrocenemethanol and vicinal oxygenated alcohols and amines is here reported. The peculiar ability of these classes of non acidic compounds to favor the dehydrative nucleophilic substitution is attributed to the presence of vicinal oxygen atoms to the reactive group able to build a hydrogen bonding network with the reactant. The role of carbon dioxide and hexafluoroisopropanol was investigated to support the hypothesis that a template catalysis effect is occurring. The in vitro anti-fungal activity of some of these derivatives was tested on two plant fungi, Botrytis cinerea and Penicillium species, with moderate activity.

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Reference:
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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Shaped carbon nanomaterials (SCNMs) were synthesized via the chemical vapour deposition (CVD) technique by using typical metallocenes (ferrocene, nickelocene, cobaltocene, and ruthenocene), and more interestingly, by use of novel ferrocenyl imidazolium derivatives, containing -Cl (FcImCl), -NO2 (FcImNO2) and -CH3 (FcImCH3) substituents as catalysts. Acetonitrile was applied both as a carbon and nitrogen source at temperatures 800?900 C. The SCNMs, namely, carbon nanotubes (CNTs), carbon spheres (CS), carbon fibres (CF) and amorphous carbons (ACs) were obtained in varying ratios depending on the catalyst and carbon sources. The ferrocenyl imidazolium catalysts produced nitrogen-doped CNTs (N-CNTs) with bamboo-like structures. The yields of various reactions were temperature-dependent, with the highest amount of N-CNTs obtained at 850 C. In all samples, the composition was mainly of CS and N-CNTs except for nickelocene at 800 C that gave CFs as a ?minor? product. Ferrocene and nickelocene in acetonitrile produced well-aligned N-CNTs while cobaltocene and ruthenocene gave ‘spaghetti-like? structures. In the case of ferrocenyl imidazolium catalyst, a coiled N-CNTs morphology was produced from FcImCl catalyst. Also, higher percentage of N-CNTs with traces of CS were obtained from the FcImCl and FcImCH3 catalysts in acetonitrile at 850 C, while higher percentage of CS and AC were obtained for FcImNO2 catalyst. In all the catalysts, the use of acetonitrile promoted nitrogen-doping (samples with more disordered and with smaller outer-diameters). Thus, this study demonstrates that the synthesis of N-CNTs from nitrogen-containing ferrocenyl imidazolium compounds as catalyst sources, provided higher percentage of N-CNTs which can be suitable for various application.

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Reference:
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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The syntheses and characterization of two new redox active cyclam ligands ferrocenylmethyl-(6-methyl-1,4,8,11tetraazacyclotetradec-6-y1)-amine (L3) and 1,1′-ferrocenylmethyl-bis(6-methyl-1,4,8,11-tetraazacyclotetradec-6-yl)-amine (L4) are reported. The compounds each possess a ferrocenyl group bearing one (L3) or two (L4) appended macrocycles linked by their exocyclic amino groups and the crystal structures of both compounds have been determined. Anion binding of L3 and L4 was investigated by electrochemical titrations where H-bonding to each macrocycle causing a shift in the Fc+/0 redox potential was used as a reporter of guest binding. The ZnII complex of L3 has also been isolated and characterized structurally. These compounds were analysed for their capacity to electrochemically recognize anions in both aqueous and non-aqueous solution, We have found that L3, L4 and [ZnL 3]2+ sense Cl- and AcO- anions in MeCN-CH2Cl2, a function that is lost in aqueous solution.

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Reference:
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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The invention relates to a double-a silicon oxygen radical three carbon ester ferrocene monomer and its preparation method. Double-a silicon oxygen radical three carbon ester ferrocene monomer the chemical structural formula of I shown in the following: the double a silicon oxygen radical three carbon ester ferrocene preparation method of the monomer is 1, 1′ – double-aldehyde ferrocene and 1 – methoxy – 1 – (trimethyl siloxy) – 2 – methyl – 1 – propene in the final ether complex as catalyst under the conditions of the double-a silicon oxygen radical three carbon ester by the reaction of the ferrocene monomer. The invention preparation of double-a silicon oxygen radical three carbon ester ferrocene monomer can be applied to the preparation of an electrically conductive material. (by machine translation)

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Reference:
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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Mixed self-assembled monolayers (SAMmix) were formed by 2-(Pyridin-2-yliminomethyl)-phenol (HL) and 1-dodecanethiol (DT) molecules on copper surface. The inhibitive ability of SAMmix in sodium chloride solution was characterized in situ by the scanning electrochemical microscope (SECM). The results show that the compactness and the stability of SAM mix, formed by the two organic materials in an appropriate sequence, are improved and the inhibition efficiency (eta%) increases markedly. They also verify that SAMmix are formed due to the existence of collapsed sites and pinhole defects on SAMs of single materials on the surface of copper. The re-arrangement and the competitive adsorption of HL and DT molecules may have impact on the quality of SAMmix. Possible structures of SAM mix are suggested based on the experimental results.

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Reference:
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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The redox potentials of electroactive species are significantly influenced by the solvation characteristics of the medium. This is manifested in the shift of half-peak potentials with the change in the solvent medium. There have been many approaches till date, both experimental and theoretical to understand the role of molecular solvents in the peak potentials of redox species. The electrochemical studies reported here are aimed at understanding the effect of deep eutectic solvents (DESs) which is distinct from conventional solvents in terms of highly concentrated ionic composition, on the half-peak potentials of some standard redox reactions. The redox species selected for this study are distinct either in terms of their charge [Fe(CN)64-/3-, Ru(NH3)62+/3+, and ferrocene methanol, FcMeOH0/+] or their hydrophilic/hydrophobic properties [methyl viologen and ferrocene]. The redox potentials are compared with the values obtained in the aqueous medium which is very well characterized in terms of solvent reorganization energy and free-energy changes. The cyclic voltammetric behavior of the redox species in DES is significantly different from that of aqueous medium. The diffusion coefficients of the redox species in DES measured by EIS and cyclic voltammetry showed significant deviations from that predicted by Stokes-Einstein equation, indicating the dominant effect of Coulombic interactions within the components of DES.

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Reference:
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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We have synthesized a series of novel SERMs bearing a ferrocenyl unit based on a three-dimensional oxabicyclo[2.2.1]heptene core scaffold. These compounds displayed high receptor binding affinities as well as ERalpha or ERbeta selectivity. In cell proliferation assays, we found that these ligands were cytotoxic at micromolar concentrations in both ER-positive and ER-negative breast cancer cells. On further examination, we found that the antiproliferative effects of compounds 9b, 10h and 11b on MCF-7 cells line does not arise from antiestrogenicity, but rather proceeds through a cytotoxic pathway. Possible mechanisms for the unique activities of these ligands were also investigated by molecular modeling. These new ligands could act as scaffolds for the development of novel anti-breast cancer agents. The Royal Society of Chemistry 2012.

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Reference:
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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The microfabrication and characterization of glass surfaces patterned with enzymes (diaphorase, horseradish peroxidase(HRP)) or antigen-antibodies (carcinoembryonic antigen (CEA), human chorionic gonadotropin (HCG) and human placental lactogen (HPL)) were studied using scanning electrochemical microscopy (SECM). Localized enzymes and antigen-antibody complexes with labeled enzymes were characterized on the basis of detection of catalytic current for ferrocenylmethanol by SECM. The SECM technique was extended to the enzyme-linked immunosorbent assay (ELISA). This method detects as low as ? 104 CEA molecules in a single microspot. We also demonstrated a novel dual assay using microfabricated glass substrates with anti-HCG and anti-HPL microspots.

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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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PROBLEM TO BE SOLVED: To provide a novel method for producing a silylamine, which uses a catalyst comprising an iron complex containing no molybdenum.SOLUTION: There is provided the method for producing a silylamine, which includes forming a silylamine represented by formula N(SiRRR)(In the formula, R, R, and Rare each independently selected from the group consisting of hydrogen and a C- Clinear, branched, or cyclic hydrocarbon group) by reacting a nitrogen gas with a silyl halide represented by formula SiRRRX (In the formula, R, R, and Rare each independently selected from the group consisting of a hydrogen atom and a C- Clinear, branched, or cyclic hydrocarbon group, and X is a halogen atom) in the presence of a catalyst which comprises an iron complex containing iron but not containing molybdenum, and a reducing agent.

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Reference:
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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In this paper, we have investigated the reactivity of the molybdenum oxide film toward some standard redox systems (e.g., ferrocene (Fc) and its derivatives) and observed a few interesting phenomena. The results demonstrate that the electrochemical behaviour of Fc and its derivatives at the oxide-modified carbon fiber (CF) microelectrode differs from that at a bare CF microelectrode. The conductivity of the molybdenum oxide film is seriously affected by the range and the direction of the potential scan, which influences the electrochemical behaviour of these redox systems at the film electrode. If the cycling potential is more positive than the reduction potential of the molybdenum oxide film, the reduction and oxidation peak currents of Fc and its derivatives could not be observed. The result indicates that the molybdenum oxide film on a microelectrode surface cannot transfer electrons between the surface of the electrode and Fc or its derivatives due to the existence of a high resistance between the interface in these potential ranges. On the other hand, if the lower limit of the scan potential was extended to a potential more negative than the reduction peak potential of the film, the oxidation peak of Fc or its derivatives appeared at about the potential relative to Eo of Fc or its derivatives on the bare electrode, and the peak current is proportional to the concentration of these couples in the electrolyte. To our surprise, the peak height on the modified electrode is much larger than that on the bare CF microelectrode under the same conditions in the range of low concentration of these couples, and the oxidation peak potential of these couples is more negative than that on the bare CF microelectrode. On the basis of the experimental observation, we propose that these redox couples may undergo an interaction with the reduction state of the molybdenum oxide film. The new phenomena that we observed have been explained by using this interaction.

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Reference:
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