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The interplay between mechanical stresses and electrochemical reactions may lead to stress corrosion cracking or hydrogen embrittlement for many materials. In this work, the effect of the tensile stress on the electrochemical properties of AISI 304 stainless steel was studied using scanning Kelvin probe (SKP) in air and scanning electrochemical microscopy (SECM) in an aqueous 0.5 M Na2SO4 electrolyte. The measurements were performed under load- and load-free conditions. No influence of the elastic stress on the electrochemical potential of the steel was found. In contrast, the plastic strain induces dislocations and dislocation pile-ups, which emerge to the surface. The formation of new active surfaces is accompanied by an increase in the roughness and a 150?200 mV decrease in the steel potential. After activation, the potential increased due to passivation of the emerging surfaces by a newly grown oxide film, which took place under both the load and load-free conditions and followed a time dependence of ? = A log t + B. Formation and then passivation of the new surfaces increased and then decreased the reduction current of the mediator in the SECM measurements. The effect of residual stress stored in the steel due to the development of dislocations on the reactivity of the re-passivated surface was investigated.

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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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Concurrent mapping of chemical reactivity and morphology of heterogeneous electrocatalysts at the nanoscale allows identification of active areas (protrusions, flat film surface, or cracks) responsible for productive chemistry in these materials. Scanning electrochemical microscopy (SECM) can map surface characteristics, record catalyst activity, and identify chemical products at solid-liquid electrochemical interfaces. It lacks, however, the ability to distinguish topographic features where surface reactivity occurs. Here, we report the design and fabrication of scanning probe tips that combine SECM with atomic force microscopy (AFM) to perform measurements at the nanoscale. Our probes are fabricated by integrating nanoelectrodes with quartz tuning forks (QTFs). Using a calibration standard fabricated in our lab to test our probes, we obtain simultaneous topographic and electrochemical reactivity maps with a lateral resolution of 150 nm.

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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 study is on current developments concerning ferrocene (FC) and its derivatives on the basis of electrochemical biosensors and sensors. The distinct physiochemical characteristics of FC have enabled the development of new sensor devices, specifically electrochemical sensors. Several articles have focused on the implementation of FC as an electrode constituent while discussing its electrochemical behavior. Furthermore, typical FC-design-based biosensors and sensors are considered as well as practical examples. The favorable design of FC-based biosensors and general sensors needs adequate control of their chemical and physical characteristics in addition to their surface immobilization and functionalization.

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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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Ferrocenylmethanol acrylate (FcMA)-immobilized polystyrene latex particles were synthesized by copolymerizing FcMA and styrene in the presence of polystyrene latex suspensions with eight different diameters ranging from 0.084 to 1.7 mum. The amounts of the ferrocenyl moiety loaded on one particle were proportional to the radii, a. The proportionality suggests the uniform distribution of the ferrocenyl moiety over the particle, of which concentration was 0.18 M. The aqueous suspensions, which were stable in the presence of a surfactant, exhibited reversible voltammetric waves for the ferrocenyl moiety. The peak current was controlled by diffusion of the latex particles. The efficiency of the reaction was obtained from the ratio of the observed current to the theoretical one which was estimated from the number of the ferrocenyl moieties and the diffusion coefficient of the particle by the Stokes-Einstein relation. The ratio was proportional to a-0.47, whereas it might be a0 for an ideal particle without any size effect. This relation was explained in terms of the contribution of rotational diffusion of redox particles.

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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 electrochemical kinetics for the oxidation of ferrocenemethanol (FcCH2OH) over the whole composition range of dimethyl sulfoxide (DMSO)-water solutions of different viscosities (I·) containing 50.0 mM (CH3)4NClO4 (TMAP) at a Pt microelectrode was studied using scanning electrochemical microscopy (SECM). The measured diffusion coefficient, DFcCH2OH, as well as the standard rate constant of the heterogeneous electron transfer, k0, as a function of solution composition, showed a minimum at about a DMSO molar fraction (xDMSO) of 0.33, corresponding to the mixture with the maximum solution viscosity. The largest k0 value found, 2.06 A± 0.31 cm s-1 in pure water (electrolyte) medium, was about 15 times larger than that obtained in the solution of xDMSO = 0.33 (0.14 A± 0.02 cm s-1). A good linear correlation between ln k0 and ln I· was observed within the solution composition range of 0.10 a¿¿ xDMSO a¿¿ 0.60. An excellent linear correlation between ln k0 and ln I¿L, the longitudinal relaxation time, was also obtained with a slope equal to 1.0 when xDMSO = 0-0.60. Unusually small rate constants found in the solutions of xDMSO a¿¥ 0.70 were attributed to adsorption effects at the tip and the substrate electrode. The k0 obtained for the present system was generally found to be inversely proportional to the viscosity of the solution and directly proportional to the diffusion coefficient of the electroactive species.

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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 article, we report the noncovalent linkage of terminal substituted oligo(dimethylsiloxanes) bearing cyclodextrins (CD) as host endgroups and adamantan or ferrocene, respectively, as guest endgroups. Structural characterization was performed by 1H NMR-, IR-, and mass spectroscopy. Electron microscopy studies show significant differences in the surface structure of the individual derivatives. In addition, the ferrocene-terminated di-and poly(dimethylsiloxanes) are distinguished by a red-ox activity and reversibility, which also makes the complexes between the ferrocene- and CD functionalized siloxanes switchable via electrochemical stimuli. The evidence for a successful complexation of the end groups, and thus the successful supramolecular formation of the siloxane strands, was even performed by shift of the protons in the 1H NMR spectra.

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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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Grinding of 1,1?-ferrocenedicarboxaldehyde with a 2.2 molar equivalent of an aromatic amine in a solvent-free environment provided excellent yields of 1,1?-ferrocenyldiimines. After mixing the aldehyde and amines, a gum or melt formed which eventually solidified to the product. An analytically pure sample of the product was obtained by cold recrystallization. Grinding of ferrocenecarboxaldehyde and 4-substituted phenylacetonitriles under solvent-free conditions provided good yields of the corresponding ferrocenylacrylonitriles. The yield in this reaction was very low when the substituent group para to the acetonitrile group was electron-donating.

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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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Alkylation reactions of [Pt2(mu-S)2(PPh 3)4] with haloalkylferrocenes FcCH2Cl, Fc(CH2)6Br and Fc(CH2)11Br [Fc = (eta5-C5H5)Fe(eta5-C5H4)] gave the cationic mu-thiolate complexes [Pt2(mu-S){mu-S(CH2) nFc}(PPh3)4]+ (n = 1, 6, 11), isolated as PF6 and/or BPh4 salts, and characterised by ESI mass spectrometry, NMR spectroscopy, microelemental analysis, and by an X-ray structure determination on [Pt2(mu-S){mu-SCH2Fc} (PPh 3)4]PF6. The complex contains the typical folded {Pt2(mu-S)2} core with an axial ferrocenylmethylthi-olate ligand. The corresponding selenolate complex [Pt 2(mu-Se){mu-SeCH2Fc}(PPh3) 4]+ was similarly obtained by alkylation of [Pt 2(mu-Se)2(PPh3)4] with FcCH 2Cl, and isolated as PF6 and BPh4 salts. The attempted liberation of FcCH2SH from [Pt2(mu-S){mu- SCH2Fc}(PPh3)4]+ using Na 2S was not successful.

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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 d4 halide complexes [MX(CO)(eta-RCCR)Tp?] {X = F, Cl, Br or I; R = Me or Ph; M = Mo or W; Tp? = hydrotris(3,5- dimethylpyrazolyl)borate} undergo one-electron oxidation to the d3 monocations [MX(CO)(eta-RCCR)Tp?]+, isolable for M = W, R = Me. X-Ray structural studies on the redox pairs [WX(CO)(eta-MeCCMe)Tp?] z (X = Cl and Br, z = 0 and 1), the ESR spectra of the cations [WX(CO)(eta-RCCR)Tp?]+ (X = F, Cl, Br or I; R = Me or Ph), and DFT calculations on [WX(CO)(eta-MeCCMe)Tp?]z (X = F, Cl, Br and I; z = 0 and 1) are consistent with electron removal from a HOMO (of the d4 complexes) which is pi-antibonding with respect to the W-X bond, pi-bonding with respect to the W-C(O) bond, and delta-bonding with respect to the W-Calkyne bonds. The dependence of both oxidation potential and nu(CO) for [MX(CO)(eta-RCCR)Tp?] shows an inverse halide order which is consistent with an ionic component to the M-X bond; the small size of fluorine and its closeness to the metal centre leads to the highest energy HOMO and the lowest oxidation potential. In the cations [MX(CO)(eta-RCCR)Tp?] + electronegativity effects become more important, leading to a conventional order for Cl, Br and I. However, high M-F pi-donation is still facilitated by the short M-F distance. The Royal Society of Chemistry.

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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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High-spin iron(III) porphyrins in frozen solutions show extra e.s.r. signals, in addition to the well known parallel (g = 2) and perpendicular (g = 6) absorption, which are remarkably sensitive to the concentration, solvent composition, pH, or the temperature.For example, two signals with g values around 3 and 11, respectively, are observed in moderately concentrated solutions of chloro(meso-nitro-octaethylporphyrinato)iron(III), in neutral and alkaline solutions of hemin when methanol is added, or in acidic solutions of tetrasodium phenylporphyrin-tetrasulphonatoferrate(III).The signals to higher field with g ca. 3 are interpreted as belonging to a dimeric species, on the basis of a simulation made by assuming a structure having two porphyrin planes arranged parallel.Another charasteristic signal, which was observed in alkaline solutions of hemin or the tetrasodium ferrate, appears as a pair of shoulders with the g = 6 monomer peak in the middle.This type of signal is assigned to a dimer having a large Fe-Fe distance as well as skew angle.The effect of adding methanol, ethanol, or sucrose to the alkaline solutions of hemin, inducing further additional signals, and that of NaCl addition, which suppresses the overall intensity, are described and discussed in relation to previous studies by spectrophotometric and magnetic susceptibility measurement.

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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