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The synthesis and solution redox properties of several covalently attached ferrocene and tetrathiafulvalene units are reported, together with the X-ray crystal structure of a 1,1′-bis(1,3-dithiole-2-ylidene)-substituted ferrocene derivative.

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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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Matrix materials, such as sol-gels and polymers derivatives to contain a redox active material can be used to form electrodes and probes suitable for use in pH meters and other analyte sensing devices.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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We investigate the Faradaic currents of ferrocene species at an electrode-membrane-electrode system. The membrane electrodes system is fabricated by physical sputtering of conductive metal on both sides of a nanoporous alumina membrane. The metal coatings function as working electrodes by connection to a bipotentiostat and reference/counter electrodes in the sample solution. Collection and shielding efficiency studies are carried out at this membrane electrodes system to measure mobility values of charged ferrocene species within nanochannels of alumina membrane. Results indicated high selective electrode response of up to 16 times for positively charged (dimethylaminomethyl)ferrocene (FcN), and neutral ferrocenemethanol (FcMeOH), compared to the negatively charged ferrocenecarboxylic acid (FcCOOH) when the receiver electrode was maintained at negative potentials of 0.5-1.0 V relative to the feed electrode. This is a report on the use of an electrode-membrane-electrode system to achieve selective response towards differently charged redox species, under the condition of high electrolyte concentration (0.1 M, pH 7.0 phosphate buffer).

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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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Suitably blocked carbohydrates containing free thio 4, amino 5, and hydroxyl 10,19 nucleophilic functionalities have been treated with (a) ferrocenecarbonyl chlorides 2 and 3. (b) N,N-dimethylaminomethylferrocene methiodide 12, and (c) ferrocenyl tosylate 16 to form the ferrocenyl sugar derivatives 6,7,8,9,11,13,14,15 and 20.Direct conjugation of a free, water-soluble sugar to ferrocene was achieved by the formation of a Schiff’s base between glucosamine hydrochloride 25 and ferrocene carboxaldehyde 24.The synthesis of ferrocenyl sugars using bridging group technology is exemplified by the conjugation of the thio sugar 4 to ferrocene via the versatile coupling reagent cyanuric chloride 21 to form the s-triazine compound 23.These products have been studied by 1H nmr spectroscopy: chemical shifts, coupling constants, and proton spin-lattice relaxation measurements.

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A cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted alpha-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C?B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the alpha-arylalkylferrocenes compounds were also obtained on a multi-gram scale.

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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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Mononuclear Zr complexes CpZrCl2{eta5-C 5H4(CH2)nCH=CH2} (n = 1, 2, 3) undergo intermolecular metathesis of the vinyl group catalyzed by a Ru complex to produce dinuclear complexes with bridging ligands, (CpZrCl 2)2 {mu-eta5-eta5-C 5H4(CH2)nC5H 4}. Hydrogenation of the products catalyzed by Pd/C affords complexes with a flexible polymethylene chain that bridges two Cp2ZrCl 2 groups. A dinuclear complex with a bridging bisfluorenyl ligand, (CpZrCl2)2(mu-eta5,eta5-C 13H8CH2CH=CHCH2C13H 8), is also obtained from the metathesis of a mononuclear Zr complex with the allylfluorenyl ligand. X-ray crystallography of (CpZrCl 2)2(mu-eta5,eta5-C 13H8CH2CH=CHCH2C13H 8) revealed the molecular structure with a trans-C=C double bond and the two Zr centers situated at different sides of the bridging bisfluorenyl ligand. Cross metathesis reaction of CpZrCl2{eta5-C 5H4(CH2)2CH=CH2} and ferrocenylmethyl acrylate produces the Zr/Fe dinuclear complex CpZrCl 2{mu-eta5,eta5-C5H 4(CH2)2-CH=CHCOOCH2C 5H4}FeCp. The dinuclear complexes catalyze polymerization of ethylene and propylene in the presence of MAO (methylaluminoxane). The activity of the Zr/Zr dinuclear complexes for ethylene polymerization is higher than that of the mononuclear precursors. The length and flexibility of the bridging group of the biscyclopentadienyl ligand also influence the catalytic activity.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Organometallic Ru(II)-cymene complexes linked to ferrocene (Fc) via nitrogen heterocycles have been synthesized and studied as cytotoxic agents. These compounds are analogues of Ru(II)-arene piano-stool anticancer complexes such as RAPTA-C. The Ru center was coordinated by pyridine, imidazole, and piperidine with 0-, 1-, or 2-carbon bridges to Fc to give six bimetallic, dinuclear compounds, and the properties of these complexes were compared with their non-Fc-functionalized parent compounds. Crystal structures for five of the compounds, their Ru-cymene parent compounds, and an unusual trinuclear compound were determined. Cyclic voltammetry was used to determine the formal MIII/II potentials of each metal center of the Ru-cymene-Fc complexes, with distinct one-electron waves observed in each case. The Fc-functionalized complexes were found to exhibit good cytotoxicity against HT29 human colon adenocarcinoma cells, whereas the parent compounds were inactive. Similarly, antibacterial activity from the Ru-cymene-Fc compounds was observed against Bacillus subtilis, but not from the unfunctionalized complexes. In both cases, the IC50 values correlated quantitatively with the Fc+/0 reduction potentials. This is consistent with more facile oxidation to give ferrocenium, and subsequent generation of toxic reactive oxygen species, leading to greater cytotoxicity. The antioxidant properties of the complexes were quantified by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. EC50 values indicate that linking of the Ru and Fc centers promotes antioxidant activity.

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Alkylferrocenes are obtained in excellent yields by ionic hydrogenation of ferrocenyl aldehydes and ketones using sodium boranuide and trifluoroacetic acid.

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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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Herein we describe a simple approach for fabrication of microring electrodes by electroless plating a thin layer of gold on polycarbonate (PC) rods. First, the PC rod was exposed to UV light to generate carboxyl groups on the surface. After amination of the surface carboxyl groups by ethylenediamine, the rod was sequentially immersed in HAuCl4 and NaBH4 solutions to form a layer of gold nanoparticles. These gold nanoparticles then functioned as the catalytically active centers for electroless plating thin gold film on the PC rod surface. Finally, the rod surface was thoroughly covered by an insulating glue and fresh microring surface could be obtained easily by laterally cutting with a knife. The electrochemical behavior of thus prepared microring electrodes were characterized by cyclic voltammetry in hydroxymethylferrocene and H2SO4. The whole fabrication process is simple and economic, which can be carried out in ordinary laboratories. In addition, the results of electrocatalytic oxygen reduction demonstrated that the proposed microelectrode could be used as an alternative electrode materials for electrocatalysis and electroanalysis.

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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