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The compound Mn(CO)5Fc can be prepared by the reaction of Mn(CO)5Br with ferrocenyllithium, FcLi.The mangana-beta-diketone H, obtained as a side-product, is converted into Mn(CO)5Fc with concomitant formation of diferrocenoyl, (FcCO)2.In proton-containing solvents the ferrocenyl group of Mn(CO)5Fc is slowly split off in the form of ferrocenylcarbonyl compounds: the aldehyde Fc-CHO is formed in acetonitrile, and the ester Fc-COOCH3 in methanol.The ferrocenyl-manganese complex, Mn(CO)5Fc, reacts with triphenylphosphane to give cis-Mn(CO)4(PPh3)Fc, with t-butylisocyanide to give fac-Mn(CO)3(CNtBu)2COFc, and with oxidants such as NOBF4 or iodine to give the ferricenium cation +.

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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 study, glassy carbon electrode modified with nano gold-crystal violet film has been used to detect arsenite (As (III)) in a model system and in groundwater samples. The modified electrode was characterized by scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). Using voltammetric measuring technique, linear response was obtained in a concentration range of 2.0?22.0 muM. The arsenite concentrations in groundwater samples varied between 2.4 muM to 4.8 muM. The sensitivity of the modified electrode for As (III) detection was 5.6 muA/muM cm2 and 0.8 muM concentration was found as lower limit of detection (LOD). The accuracy of the method was checked with standard method anodic stripping voltammetry (ASV). Groundwater samples were characterized with dynamic (DLS) and electrophoretic (ELS) light scattering measurements which have shown that particles present in different samples differ in size distribution and zeta potential which did not interfere with As (III) detection.

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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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Chlorophyll a is known as the prevailing light absorbing pigment giving a strong absorption and fluorescence emission in visible region. Quenching reactions of the chlorophyll a fluorescence by Fe(acac)3 were precisely investigated in various organic solvents which are benzene toluene, ethanol, methanol, dmf, dmso and acetonitrile. Electron transfer performance of chlorophyll a by Fe(acac)3 was investigated from oxidative quenching reaction. Herein, the simplified Rehm-Weller relationship was used to calculate the free energy change of the photo-induced electron transfer reaction. Emission intensity decreased when the concentration of Fe(acac)3 quencher was increased. Non-linear Stern-Volmer plots are found to be affected by inner filter effect more than the ground state complex formation. Rate of quenching reactions (kq) were determined from the Stern-Volmer equation with corrected inner filter effect. The rates of quenching reactions occurred faster in high viscous solvents.

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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 benzoquinone modified basal plane pyrolytic graphite electrode shows electrocatalytic activity for the oxidation of NADH and ascorbic acid in phosphate buffer (pH 7.3). The modified electrode shows a linear variation of catalytic current with concentration in the range 1-10 mM for both NADH and ascorbic acid. The rate constants have been estimated from the surface coverage data.

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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 electrospray ionization behavior of some ferrocenylalkylazoles CpFeC5H4CH(R)Az (AzH are derivatives of imidazole, pyrazole, triazole and their benzo analogs; R = H, Me, Et, Ph), ferrocenylalkanols CpFeC5H4CH(R)OH (R = H, Me), and mixtures of the latter with azoles was studied. The electrospray ionization mass spectra of these compounds, in addition to the molecular ion [M] +·, the protonated molecule [M + H]+, and ferrocenylalkyl cation [FcCHR]+ peaks, exhibit also intensive peaks for the binuclear ions [(FcCHR)2X]+ (X = Az or O), resulting from ferrocenylalkylation of the initial compounds with the ferrocenylalkyl cations. Electrospray ionization of an equimolar mixture of ferrocenylmethanol FcCH2OH and imidazole gives the protonated ferrocenylmethylimidazole molecule [FcCH2Im + H]+ and the [FcCH2(Im)2 + H]+ dimer, apart from the ions typical of each component, i.e., ferrocenylalkylation of azoles with the ferrocenylalkylcarbinols, known in the chemistry of solutions, takes place under electrospray conditions.

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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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Ultramicroelectrode (UME) tips from conductive diamond were fabricated by hot filament chemical vapour deposition. By changing growth conditions, it was possible to fabricate tips with very smooth nanocrystalline coatings, or relatively rough microcrystalline deposits. Cyclic voltammetry data in ferrocene methanol solution was recorded to characterise the two types of diamond. Nanocrystalline diamond displayed inferior behaviour, both in terms of the potential window, and the background current. Two types of insulation method were studied to complete the microelectrode fabrication process. Nail varnish was found to be easiest to apply and produce the best results. Fast set epoxy produced electrodes with inferior voltammetric characteristics. Electrochemical approach curves were measured under differing conditions for the electrodes studied.

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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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Local electrochemical techniques such as scanning electrochemical microscopy, scanning vibrating electrode technique, local electrochemical impedance spectroscopy, scanning Kelvin probe technique, and scanning ion-selective electrode technique have gained significant attention in organic coating research. These techniques have enhanced our understanding of the fundamental processes of corrosion at defects and underneath coatings. Each of these techniques employ unique measurement strategy to provide important local information about coatings, their protective properties, defects, and failure mechanisms. In this brief review, the basic principles of these techniques and the nature of information that has been extracted from these techniques to study organic coatings 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

 

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The functional dependence of the rate constants for self-exchange, kex, for a series of metallocene redox couples to solvent-induced variations in the nuclear frequency factor, nun, engendered by alterations in the longitudinal solvent relaxation time, tauL, are utilized to deduce values of the electronic matrix coupling element, H12, for electron exchange.The analysis exploits the sensitivity of the kex-tauL-1 dependence to the degree of reaction adiabaticity and hence H12 for a given electron-exchange reaction.Six metallocene couples are examined:Cp2Co+/0, Cp2Fe+/0 (Cp = cyclopentadienyl), the decamethyl derivatives Cp’2Co+/0 and Cp’2Fe+/0 scrutinized previously, with additional solvent-dependent kex values for (carboxymethyl)cobaltocenium-(carboxymethyl)cobaltocene and (hydroxymethyl)ferrocenium-(hydroxymethyl)ferrocene .Kinetic data are examined in 15 solvents, including 11 “Debye” solvents for which it is anticipated that nun <*> tauL-1.Corrections to kex for the solvent-dependent variations in the barrier height were obtained by corresponding measurements of the optical electron-transfer energies for the related binuclear complex biferrocenylacetylene, yielding “barrier-corrected” rate constants, k’ex.The k’ex-tauL-1 dependencies, as well as the kex values in a given solvent, are markedly dependent on the redox couple.The log k’ex-log tauL-1 plots for the most facile couple, Cp’2Co+/0, exhibit slopes approaching unity for smaller tauL-1 values.The less facile couples yield smaller slopes, diminishing in the same sequence that k’ex decreases in a given solvent: Cp’2Co+/0 >Cpe2Co+/0 > Cp2Co+/0 >/= Cp’2Fe+/0 > Cp2Fe+/0 >/= HMFc+/0.These findings are consistent with H12 decreasing in the same order.Comparison of such rate-solvent friction dependencies with corresponding plots calculated using a combined solvent friction-electron tunneling model yields the following approximate values of the matrix coupling element for reactant “closest approach”, H012 (kcal mol-1): Cp’2Co+/0, 1.0; Cpe2Co+/0, 0.5-1.0; Cp2Co+/0, 0.5; Cp’2Fe+/0, 0.2; Cp2Fe+/0, 0.1; HMFc+/0, 0.075.Reasonable concordance is seen with recent theoretical estimates of H012 for Cp2Co+/0 and Cp2Fe+/0.The relationship between H012 and metallocene electronic structure is briefly discussed.The analysis also enables effective solvent relaxation times for adiabatic barrier crossing in non-Debye media, including primary alcohols, to be extracted.

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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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Coordinative directed assembly has been used by a number of research groups to obtain molecular squares featuring porphyrin components. The syntheses and functional behavior of these compounds are reviewed.

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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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Cellulose nano-whiskers or nanocrystals are used as a carbon source in a vacuum graphitisation process to surface-modify nano-TiO2 and influence its photoreactivity. In sharp contrast to bulk carbon-modified TiO2 materials, introducing cellulose in a controlled way, i.e., a layer-by-layer deposition process, allows thin film materials to be created with low graphite content, but with strongly suppressed responses to light. The effect is explained by highly effective surface recombination and demonstrated for the I3-/I- redox system in acetonitrile and for the photo-oxidation of acetate in aqueous media.

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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