Brief introduction of Ferrocenemethanol

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The iron complex [Fp][OTf] {Fp+ = [Fe(CO)2(Cp)] +, OTf- = SO3CF3-} is an efficient catalyst for the direct substitution of the OH group in ferrocenylmethanol [Fc-CH2OH] by thiols, aromatic amines, diphenylphosphane, and carbon nucleophiles (furan, pyrrole, and indole). This approach offers a convenient route to ferrocenes containing side chains with different functional groups. The advantages of the method are associated with the use of a catalyst based on iron, which is a nontoxic and readily available transition metal, and in the direct OH substitution, which produces water as the only byproduct. Direct substitution of the OH group in ferrocenylmethanol by S, N, P, and C nucleophiles containing an active hydrogen atom (thiols, aromatic amines, diphenylphosphane, furan, pyrrole, indole) can be accomplished by use of the iron catalyst [Fe(CO)2(Cp)][OTf] (Cp = cyclopentadienyl, OTf = SO3CF3). Copyright

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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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Electroactive ionic liquids obtained by modifying imidazolium with ferrocenyl moiety and alkyl chains of different lengths (n = 1, 4, 8 and 12) were studied in their pure form and dissolved in ethylene/diethylene carbonates (EC/DEC) solvent. Bis(trifluoromethanesulfonyl) imide (TFSI) was used as the anion. The conductivity of the pure ionic liquids (0.1 to 0.04 mS cm?1) was found to decrease with the increase in alkyl chain length as expected from larger van der Waals interactions. The conductivities of carbonate solutions of redox ionic liquid (50% vol.) were less affected by the chain length but were strongly dependent on the presence of Li ions due to their coordination with TFSI, providing viscous solutions (86-111 cP) which decreased the self-diffusion of the redox imidazolium by a factor of 6. The equilibrium potential of the RIL dissolved in the carbonate solvent was not affected by the alkyl chain length, but mass transport by migration caused a distortion in cyclic voltammograms for highly concentrated solutions.

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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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With the emerging interest in layered transition metal dichalcogenides (TMDs), MoS2 has occupied a unique place in recent times as graphene (GR) analog. Development of novel state of the art electrochemical approaches at MoS2 modified working surfaces is an upcoming field and holds great promise for design and development of next generation sensing devices. Large available surface area, high biocompatibility and structural versatility of 2D/3D MoS2 nanostructures have produced numerous hybrid sensors and biosensors which have demonstrated their prominent role in biological, environmental, pharmaceutical, chemical, industrial and food analysis. A comprehensive and critical detail of recent advancements of MoS2 based sensors for real time applications have been presented in the present review. Overall conclusion related to sensing performances of MoS2 nanostructures and future needs to further exploit the unusual properties of mono and few layer of other TMDs for developing advance recognition systems have been concluded at the end.

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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 diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes-Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle.

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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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Comparative analysis of the specific features of autooxidation of ferrocenylacetic acid (FcCH2COOH) in organic solvents at 30-50C in the absence and in the presence of trifluoroacetic acid (processes 1 and 2 respectively) was carried out. It was shown that both reactions proceed as a sequence of two macrostages, the molecular and the chain radical oxidation of the metal complex. Introduction of acid (HX) in the reaction mixture leads to a significant increase in the rate of the process, in the amount of oxygen per one mole of metal complex absorbed by the reaction mixture, and to the change in the yields of main reaction products like hydroxymethylferrocene, formylferrocene, ferrocenylpyruvic acid, and CO2. On the basis of results of the investigation performed, the kinetic and thermodynamic analysis of primary reactions of the process probable mechanisms of both macrostages in both processes were suggested. The significant effect of approach and orientation on the rate of the molecular oxidation of complex as the bifunctional reagent was noted. An assumption was made that the acid takes place in the molecular oxidation of FcCH2COOH according to two alternative mechanisms differing by the way of its coordination with O2 and the metal complex in the prereactional intermediates. The oxidative transformation of these intermediates leads to the generation of radicals of different nature, Fc+?CH2C(O)OO? and HO 2 ? which initiate the chain radical oxidation of the metal complex.

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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 unusual nonbifunctional outer-sphere strategy was successfully utilized in developing an easily accessible N-heterocyclic carbene manganese (NHC-Mn) system for highly active alpha-alkylation of ketones with alcohols. This system was efficient for a wide range of ketones and alcohols under mild reaction conditions, and also for the green synthesis of quinoline derivatives. The direct outer-sphere mechanism and the high activity of the present system demonstrate the potential of nonbifunctional outer-sphere strategy in catalyst design for acceptorless dehydrogenative transformations.

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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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This account focuses on the application in catalysis of ruthenium and osmium complexes containing 2-(aminomethyl)pyridine (Ampy)-based ligands. The combination of these aminoalkylpyridine ligands with appropriate phosphines affords ruthenium and osmium systems displaying unprecedented high catalytic activity and productivity in a variety of organic transformations such as hydrogenation by hydrogen transfer and dihydrogen, dehydrogenation, racemization, and alkylation.

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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 discloses a novel containing nitrogen oxygen free radical ferrocene derivatives preparation method and use thereof, of formula (I) is shown containing nitrogen oxygen free radical of the ferrocene derivative or its pharmaceutically acceptable salt or pharmaceutical composition or solvate. (I) in formula (I) indicated by the ferrocene derivative to a lung cancer cell strain A549 and breast cancer cell MCF – 7 of value-added has very strong inhibiting activity, can be used as a medicine for treating cancer, tumor diseases such as candidate compound or a lead compound. (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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Scanning electrochemical microscopy (SECM) can image graphene oxide (GO) flakes on insulating and conducting substrates. The contrast between GO and the substrate is controlled by the electrostatic interactions that are established between the charges of the molecular redox mediator and the charges present in the sheet/substrate. SECM also allows quantitative measurement-at the nano/microscale-of the charge transfer kinetics between single monolayer sheets and agent molecules. This journal is

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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 role played by heating in the electrochemical behavior of plasmonic nanostructures under illumination was examined through a combination of theoretical modeling and experimental investigations. A theoretical treatment of heating in plasmonic electrochemical systems was developed, which treats heat flow from arrays of nanoparticles attached to an electrode as a heat source delocalized across the electrode-solution interface. Within this framework, simple analytical expressions for the temperature profile in the vicinity of illuminated electrodes are presented for a 1D model treating heat transfer via conduction. Results from more detailed finite element simulations treating heat transfer via both conduction and convection in realistic cell geometries are also provided. Both approaches predict significant increases in the mass transfer of dissolved redox species, which can readily explain the current enhancements observed with electrodes decorated with plasmonic nanostructures under illumination. These predictions were tested experimentally by employing conventional, millimeter-sized electrodes decorated with Au nanoparticles in potential step experiments under intermittent illumination. Experiments with both outer-sphere (ferrocene methanol) and inner-sphere (hydrazine) redox couples displayed significant current enhancements due to illumination, which agreed well with theoretical predictions. Experiments at individual nanoparticles were also carried out using probe-based techniques. These measurements displayed no significant effects due to heating, attributable to efficient heat transfer away from nanoparticles in this experimental geometry. Implications of these results on research into the effects of hot charge carriers in electrochemical experiments are discussed.

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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