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Three ferrocene derivatives carrying different kinds of nitroxide radicals (1-3) were prepared as dual redox compounds. All of them have distorted molecular conformations between a Cp unit of a ferrocene group and a nitroxide group and the largest dihedral angle between the units is observed in the PO derivative 3. A unique magnetic behavior with a spin gap is disclosed in the derivative 3, reflecting two-dimensional interactions between the paired spins. Each derivative has two oxidation potentials based on both ferrocene and nitroxide groups and multi-step charge-discharge processes are found for all derivatives with the first discharge capacity over 200 A h kg-1.

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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 development of catalysts based on earth abundant metals in place of noble metals is becoming a central topic of catalysis. We herein report a cobalt/tetraphosphine complex-catalyzed homogeneous hydrogenation of polar unsaturated compounds using an air- and moisture-stable and scalable precatalyst. By activation with potassium hydroxide, this cobalt system shows both high efficiency (up to 24 000 TON and 12 000 h-1 TOF) and excellent chemoselectivities with various aldehydes, ketones, imines, and even N-heteroarenes. The preference for 1,2-reduction over 1,4-reduction makes this method an efficient way to prepare allylic alcohols and amines. Meanwhile, efficient hydrogenation of the challenging N-heteroarenes is also furnished with excellent functional group tolerance. Mechanistic studies and control experiments demonstrated that a CoIH complex functions as a strong hydride donor in the catalytic cycle. Each cobalt intermediate on the catalytic cycle was characterized, and a plausible outer-sphere mechanism was proposed. Noteworthy, external inorganic base plays multiple roles in this reaction and functions in almost every step of the catalytic cycle.

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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 biosensor based on the immobilization of lactate oxidase (LOx) on a glassy carbon electrode modified with laponite/chitosan hydrogels for the quantification of l-lactate in alcoholic beverages and dairy products is presented. Ferrocene-methanol (FcMe) is used as artificial mediator. The purpose of this work is to determine the best hydrogel composition from the analytical point of view. The characterization of the hydrogels was carried out by CV, amperometry and EIS. According to permeabilities and charge transfer resistances for ferrocyanide (used as molecular probe) as well as the enzymatic behavior of the enzyme for l-lactate, the best laponite/chitosan mass ratio found was 25/50. The distinct features of the bioelectrode are its long stability, its ability to reject or minimize most interferents including ascorbic acid, and its excellent analytical response, which allowed the reduction of the enzyme content below 0.5 U, for a sensitivity of (0.326 ± 0.003) A cm -2 M-1, with a time response lower than 5 s and a detection limit of (3.8 ± 0.2) × 10-6 M. Our l-lactate biosensor was validated by comparison with a standard spectroscopic method.

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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 report the results of a systematic electrochemical study of the host-guest supramolecular adducts between ferrocene (Fc), ferrocenium cation (Fc+), and other mono- and disubstituted ferrocene derivatives with different beta-cyclodextrins (CD) in mixed organic-aqueous media. The influence on the formation constants (Kf) of the organic cosolvent, the different substituents on Fc, and the type of CDs are evaluated. NMR and conductometry responses of ferrocenium cation solutions in the presence of CD confirm the weak propensity of Fc+ to enter into the cyclodextrin cavity. The Kf value generally decreases as the steric bulk and the rigidity of Fc substituents increases, consistent with an inclusion model in which the Fc fits into the CD cavity in an axial mode while the substituent protrudes out. Interestingly, the addition of sulfated beta-CD shifts the redox Fc/Fc+ couple toward cathodic values, indicating that the oxidized, cationic form Fc+ is more strongly bound to the sulfated cyclodextrin than neutral Fc, probably by means of electrostatic interaction with the external -SO3- functionalities.

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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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Moessbauer and NMR spectra are reported for ferrocenyl (Fc) carbenium ions, FcCH2+ (III+) and FcC+Me2 (II+) in frozen acidic media. 1H-NMR spectra showed no evidence of Fe-H bonded species.Moessbauer parameters for II+ were identical within experimental error to those obtained for the carbenium ion precursors and to ferrocene itself, whereas quadrupole splittings for III+ were significantly larger.The results for the latter species are interpreted in terms of stabilisation via orbital overlaps with the central iron atom.

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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 work deals with the synthesis and evaluation of new compounds designed by combination of 1,4-naphthoquinone and ferrocene fragments in a 3-ferrocenylmethyl-2-hydroxy-1,4-naphthoquinone arrangement. A practical coupling reaction between 2-hydroxy-1,4-naphthoquinone and ferrocenemethanol derivatives has been developed. This procedure can be carried out “on-water”, at moderate temperatures and without auxiliaries or catalysts, with moderate to high yields. The synthesized derivatives have shown significant in vitro antiplasmodial activity against chloroquine-sensitive and resistant Plasmodium falciparum strains and it has been shown that this activity is not related to the inhibition of biomineralization of ferriprotoporphyrin IX. Binding energy calculations and docking of these compounds to cytochrome b in comparison with atovaquone have been performed.

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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 paper addresses on the electrochemical behaviour of three TiMo alloys exposed to simulated physiological environments. Their stability and corrosion resistance was characterized in order to explore the potential application for the manufacturing of implant materials. Ringer’s solution together with an acidic modification of the Ringer’s solution (pH 3.1) at room temperature were considered. Both electrochemical methods (namely, potentiodynamic polarization curves and electrochemical impedance spectroscopy, EIS), and spatially resolved scanning electrochemical microscopy (SECM), were used. Additionally, surface characterization was made employing optical microscopy and scanning electron microscopy (SEM). The oxide films formed on the TiMo alloys in neutral and acidic Ringer’s solutions effectively protect the metal from dissolution in these environments, and no breakdown of the passive layer occurs in the potential range up to +1.00 V vs. SCE. SEM micrographs of retrieved samples do not show corrosion pits, cracks, or any other defects despite the rather high positive potential values reached during the potential excursion. EIS data reveal that two-layer oxide films are formed, consisting of a porous outer layer and a compact inner layer (approximately 5-6 nm thick), the latter accounting almost completely for the corrosion resistance of the materials. The corrosion resistance of the inner compact film towards metal dissolution is smaller in the acidic environment, whereas it increases with higher Mo contents in the alloy. The passive oxide films exhibit dielectric characteristics towards charge transfer when they are imaged by scanning electrochemical microscopy.

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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 typical Chinese liquor was characterised using a triple-electrode system with clean and simple design. In this approach, liquors were analysed with no other pre-treatment than mixing the liquor with a potassium chloride solution to ensure sufficient conductivity. Two broad reduction peaks at [?0.3 V, ?0.5 V] and [?0.7 V, ?0.8 V] were present in the cyclic voltammetry, demonstrating the feasibility of the gold electrode for liquor characterisation. Both the competing reactions in the liquor samples contributed to the reduction current. Thus, the steady-state microelectrode voltammetry affords an opportunity to estimate the total concentration of the redox-active species in the mixed compounds according to the relationship between the total concentration and the value of limiting diffusion current. Further, the discrimination of liquors at different ageing times was realised by the conjunction of the electrochemical results and principal component analysis.

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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 topic of intermolecular interactions enhancing electron tunneling between protein residues on biofilm surface has been investigated by some theoretical studies. However, few of experimental studies could confirm this viewpoint. In this work, the Mercaptopropionic acid self-assembled monolayer (MPA SAM) with terminal carboxyl groups was constructed, as a simplified model for functionalized biomimic membrane. The electron tunneling rate constant of ferrocenylmethanol redox process on SAM was obtained from experimental results of scanning electrochemical microscopy. It is found that the electron tunneling across MPA SAM is faster than that of contrastive Methyl mercaptopropionate SAM. This result is attributed to the intermolecular interactions between the redox and MPA molecules. The conditions of lower pH and weaker ion pair effect all benefit the formation of the intermolecular interactions, resulting the enhancement of electron tunneling more obvious. Based on this, this kind of intermolecular interaction is inferred to be intermolecular hydrogen bond. Our work may have contributions to exploring electron tunneling between protein residues on biofilm surface.

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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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n-BiVO4 is a promising semiconductor material for photoelectrochemical water oxidation. Although most thin-film syntheses yield discontinuous BiVO4 layers, back reduction of photo-oxidized products on the conductive substrate has never been considered as a possible energy loss mechanism in the material. We report that a 15 s electrodeposition of amorphous TiO2 (a-TiO2) on W:BiVO4/F:SnO2 blocks this undesired back reduction and dramatically improves the photoelectrochemical performance of the electrode. Water oxidation photocurrent increases by up to 5.5 times, and its onset potential shifts negatively by ?500 mV. In addition to blocking solution-mediated recombination at the substrate, the a-TiO2 film – which is found to lack any photocatalytic activity in itself – is hypothesized to react with surface defects and deactivate them toward surface recombination. The proposed treatment is simple and effective, and it may easily be extended to a wide variety of thin-film photoelectrodes.

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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