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The visible absorption spectra and reduction potentials of 11 ferrocenes containing electron-withdrawing substituents were determined in an N-n-butylpyridinium chloride-aluminum chloride molten salt. When the substituent(s) on the cyclopentadienyl ring(s) of ferrocene were varied, the reduction potential was caused to range over 1.25 V, and the wavelength for maximum absorption of visible light was varied by nearly 200 nm. These changes are greater than have been observed for similar ferrocenes in other nonaqueous solvents. Evidence is presented for specific interactions of particular ferrocenes with the molten salt.

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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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The catalytic hydrogenolysis of 1,2-disubstituted ferrocenes having planar chirality and functional groups such as carboxyl (including ester) or tertiary amino proceeds under mild conditions (1 atm of H2, Pd/C, CF3COOH, 50 deg C) with the retention of functional groups in the cyclopentane products.Stereosectivity has been observed for the examples investigated, the diastereomeric ratio, trans: cis being close to 4:1, but optically inactive products are formed the enantiomeric ferrocenes.In contrast, hydrogenolysis of enantiomeric alpha-(N,N-dimethylamino)ethylferrocene gives an optically active alpha-(N,N-dimethylamino)ethylcyclopentane with retention of configuration at the alpha-carbon, whose bonds are not affected during the hydrogenolysis.

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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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Treatment of ferrocenecarboxaldehyde with base at 0 deg C, lithium diisopropylamide (LDA) or n-butyllithium, followed by the addition of trimethylsilylcyanide, produced 1-(diisopropylamino)cyanomethylferrocene, FcCH(N2)(CN) (II) or 1-trimethylsiloxy-n-pentylferrocene.FcCH(nBu)OSiMe3 (IIIa).The reaction of naphthaldehyde, NpCHO, with LDA/Me3SiCN led to formation of 1-(diisopropylamino)cyanomethylnaphthalene, NpCH(CN) suggesting a general new synthesis for cyanoamines.The reaction of ferrocenecarboxaldehyde with Me3SiCN led to the expected silylether FeCH(CN)OSiMe3 (I).An alternative synthesis of ferrocenylmethylsilylethers, FeCH2OSiR3 (IV), involved the reaction of 1-ferrocenylmethanol with R3SiCl in the presence of pyridine.The basicity of the new silylethers III and IV is reported.

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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-active cyanomanganese carbonyl ligands cis- and trans-[Mn(CN)(CO)2{P(OR)3}(dppm)] (R = Ph or Et dppm = Ph2PCH2PPh2) reacted with ZnBr2, CdI2 and Hg(NO3)2 to give the tetrahedral (at M) complexes [X2M{(mu-NC)MnLx}2] [MX2 = ZnBr2, CdI2 or Hg(NO3)2; Lx = cis- or trans-(CO)2{P(OR)3}(dppm); R = Ph or Et]; similarly [Mn(CN)(NO)PPh3)(eta-C5H4Me)] gives [X2M{(mu-NC)MnLx}2] {MX2 = ZnBr2 or CdI2 Lx = (NO)-(PPh3)(eta-C5H4Me)}. Treatment of [Br2Zn{(mu-NC)MnLx}2] [Lx = trans-(CO)2{P(OEt)3}(dppm)] 4 with TlPF6 in the presence of 1 or 2 equivalents of trans-[Mn(CN)(CO)2{P(OEt)3}(dppm)] gave the tetra- and penta-metallic complexes [BrZn{(mu-NC)MnLx}3][PF6] 13 and [Zn{(mu-NC)MnLx}4][PF6]2 14 [Lx = trans-(CO)2{P(OEt)3}(dppm)] respectively. Differential pulse volammetry showed that 4, 13 and 14 are oxidised to weakly interacting mixed-valence complexes. The reaction of trans-[Mn(CN)(CO)(dppm)2] with ZnBr2 or CdX2 (X = Br or I) in thf gave the bimetallic species [X2(thf)M(mu-NC)Mn(CO)(dppm)2] (MX2 = ZnBr2 or CdI2) and [Br2Cd(mu-NC)Mn(CO)(dppm)2] which are oxidised by [Fe(eta-C5H5)2][PF6] to the MnII complexes [X2(thf)M(mu-NC)Mn(CO)(dppm)2][PF6] and [Br2Cd(mu-NC)Mn(CO)(dppm)2][PF6]. The crystal structures of the tetrahedral polynuclear complexes [I2Cd{(mu-NC)MnLx}2] [Lx = trans-(CO)2{P(OEt)3}(dppm)] 9 and [Br2(thf)Zn(mu-NC)Mn(CO)(dppm)2] 15 are reported, and the importance of steric effects (as quantified by cone angles) in the behaviour of cyanomanganese carbonyl ligands is noted.

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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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Novel ferrocene-oligothiophenylene-cyanoacrylic acid in the form of donor-spacer-acceptor dyads was synthesized. The compound with a single unit of thiophenylene showed the lowest energy transition in neutral state. For radical cations, the lowest energy transition appears red-shifted along with the increased number of thiophenylene units. These results suggested that the electronic structure of radical cations is significantly different from that of neutral molecules.

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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 enzyme pyruvate oxidase (PyOD) covalently immobilized on an original conducting copolymer poly(5-hydroxy-1,4-naphthoquinone-co-5-hydroxy-3-thioacetic-1,4-naphthoq uinone acid) can be recycled under anaerobic conditions, at +0.1 V versus SCE. It is first demonstrated that the quinone group is an efficient co-substrate for PyOD in homogeneous conditions, then this efficiency is preserved when the quinone group is embedded in the polymer structure. The copolymer remains efficient even in aerated media. The low working potential avoids side-oxidations of interfering species as ascorbic acid or salycilate.

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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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A carbon microfiber (7 mum diameter) is employed herein as an electroanalytical sensor. The fabricated sensor is cheap, is disposable, and requires only 150 muL of samples. The carbon fiber is surface-mounted onto an inert surface to overcome the problems of the fragility of the microwire and the possible interference of convective force due to the nonrigid nature of the wires, as well as to improve the reproducibility in length and the amperometric responses. As the cylindrical electrode is supported on a surface, the diffusion of redox-active species to the electrode is partially blocked by the substrate. A theoretical model is developed to account for this hindered diffusion. The mass-transport regime is altered from “linear” at very short time, where the amperometric responses of the supported microwire closely resemble that of an isolated free-standing cylinder (current alpha electrode area), to “convergent” at long time where its response now tends toward that of a hemicylinder of equal radius. The model is validated using chronoamperometry and cyclic voltammetry of an ideal outer-sphere redox probe, reversible ferrocene methanol oxidation. The fabricated microwire electrode is further applied to the system of irreversible 2-nitro-5-thiobenzoate oxidation used in the detection of reduced glutathione (GSH). The microwire electrode shows significantly higher ratio of Faradaic to non-Faradaic currents as compared to microdisk, macrodisk or carbon nanotube modified electrodes. Using the fabricated microwire, GSH can be detected with the sensitivity of 0.7 nA muM-1 and the limit of detection of 0.5 muM (3 sB/m). (Figure Presented).

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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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Introduction: Cell?cell communication plays a pivotal role in biological systems? coordination and function. Electrical properties have been linked to specification and differentiation of stem cells into targeted progeny, such as neurons and cardiomyocytes. Currently, there is a critical need in developing new ways to complement fluorescent indicators, such as Ca2+-sensitive dyes, for direct electrophysiological measurements of cells and tissue. Here, we report a unique transparent and biocompatible graphene-based electrical platform that enables electrical and optical investigation of human embryonic stem cell-derived cardiomyocytes? (hESC-CMs) intracellular processes and intercellular communication. Methods: Graphene, a honeycomb sp2 hybridized two-dimensional carbon lattice, was synthesized using low pressure chemical vapor deposition system, and was tested for biocompatibility. Au and graphene microelectrode arrays (MEAs) were fabricated using well-established microfabrication methods. Au and graphene MEAs were interfaced with hESC-CMs to perform both optical and electrical recordings. Results: Optical imaging and Raman spectroscopy confirmed the presence of monolayer graphene. Viability assay showed biocompatibility of graphene. Electrochemical characterization proved graphene?s functional activity. Nitric acid treatment further enhanced the electrochemical properties of graphene. Graphene electrodes? transparency enabled both optical and electrical recordings from hESC-CMs. Graphene MEA detected changes in beating frequency and field potential duration upon beta-adrenergic receptor agonist treatment. Conclusion: The transparent graphene platform enables the investigation of both intracellular and intercellular communication processes and will create new avenues for bidirectional communication (sensing and stimulation) with electrically active tissues and will set the ground for investigations reported diseases such as Alzheimer, Parkinson?s disease and arrhythmias.

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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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The diffusion of ferrocene methanol in super-cooled aqueous solutions containing sucrose has been studied, using disk and cylindrical microelectrodes, over a wide viscosity range. The solution viscosity and the reduced temperature T/Tg (Tg being the glass transition temperature) were varied by changing the sucrose concentration and the temperature of the system. The voltammetric limiting current obtained with a disk microelectrode and the i(t) response on a cylindrical microelectrode after a potential step were used to determine diffusion coefficients from 7 × 10-6 cm2 s-1 down to 2 × 10-11 cm2 s-1. The electrochemical procedure described in this work allows a simple and accurate measurement of the dynamics of electroactive solutes in glass-forming liquids.

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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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Borane, as a DMS or a THF complex, can efficiently reduce a large range of ferrocenyl derivatives (aldehydes, ketones, ethers, acetals, carboxylic acids, esters,…) if they bear at least one oxygen at a carbon at the alpha position. On the contrary, similar molecules, which contain nitrogen instead of oxygen, do not react with borane.

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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