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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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A series of ferrocene-containing N-allylcarbamates, CH2= CHCH2-NHCOO-(CH2)mFc with m = 1-4 and Fc = ferrocenyl, was synthesized by reacting allylisocyanate with different ferrocenylalcohols, Fc-(CH2)n-OH (n = 1-4). The electrochemistry of the carbamates was studied by cyclic voltammetry in CH 2Cl2/0.1 M NnBu4PF6 utilising a glassy carbon working electrode. The ferrocenyl group showed reversible electrochemistry with the formal reduction potential (E o? versus FcH/FcH+) of the ferrocenyl group inversely proportional to spacer chain length. The single crystal X-ray structure of the complex with m = 1 (monoclinic, P21/c space group) explained the good through bond communication that was electrochemically detected between the electron-withdrawing NHCOO group and electron-donating Fc modalities.

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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 short and efficient preparation of conjugated oligo(phenylene-ethylene) thiols bearing redox-active ferrocene moieties is described. While minimising the number of synthetic steps, the proposed strategy permits the development of sets of oligomers with varying chain length. The redox properties of the compounds in solution are determined. Preliminary studies of self-assembled monolayers (SAMs) on gold electrodes are discussed, and indicate that electron transfer through the SAMs is indeed rapid. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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 kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, FeIV(H2O)5O2+ (hereafter FeIVaqO2+), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN)32+ (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS-/ABTS2-, phenothiazines, CoII(dmgBF2)2, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generated ligand-modified products. FeIVaqO2+ oxidizes even Ce(III) (E0 in 1 M HClO4 = 1.7 V) with a rate constant greater than 104 M-1 s-1. In 0.10 M aqueous HClO4 at 25 C, the reactions of Os(phen)32+ (k = 2.5 × 105 M-1 s-1), IrCl63- (1.6 × 106), ABTS2- (4.7 × 107), and Fe(cp)(C5H4CH2OH) (6.4 × 107) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen)32+ and of ferrocenes remained unchanged in the acidity range 0.05 < [H+] < 0.10 M, ruling out prior protonation of FeIVaqO2+ and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k22 + E0Fe/0.059) = 17.2 ± 0.8, where k22 and E0Fe are the self-exchange rate constant and reduction potential, respectively, for the FeIVaqO2+/FeIIIaqO+ couple. Comparison with literature work suggests k22 < 10-5 M-1 s-1 and thus E0(FeIVaqO2+/FeIIIaqO+) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E0 (FeIVaqO2+, H+/FeIIIaqOH2+) ? 1.95 V.

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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 synthesis of homochiral phosphorus-based ligands has escalated dramatically over the last decade in the drive to develop new, and further fine tune existing, base structures of chiral auxiliaries that have had, and most certainly are continuing to have, a phenomenal impact in the arena of enantioselective catalysis. This review highlights the vast array of homochiral phosphorus-based ligands and their significantly fewer arsenic-based analogs, the key synthetic strategies used to prepare them and the significant roles that they have been employed in after coordination to a transition metal center.

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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 aim of this study is to consider the adsorption phenomena at the electrode/solution interface in systems containing complexes of cucurbit[7]uril (CB7) with organic compounds: adamantanol?1, ferrocene and organic dye 3,3??diethylthiocarbocyanine iodide. These guests form exclusively stable inclusive complexes with CB7. Experimental dependences of differential capacitance C as a function of potential were used in calculating the adsorption parameters characterizing the most important properties of adsorption layers formed by compounds under study at the electrode/solution interface. For all the systems studied here, as for those studied earlier, adsorption parameters for negative and positive charges of the electrode surface differ. Obviously this points to deep changes in the properties of adsorption layers depending on the electrode potential.

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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 stable palladium-decorated SBA-15 nanocomposite was simply fabricated through surface modification of SBA-15 with biguanide and subsequent metal/ligand coordination with Pd2+ from inexpensive commercially available starting materials and using standard laboratory techniques. The structure of this organic inorganic hybrid material was characterized by SEM, TEM, XRD, elemental analyzer, atomic absorption spectroscopy, N2 adsorption-desorption (BET), and FT-IR techniques. The catalytic performance of this novel heterogeneous catalyst was determined for the Suzuki cross-coupling and aerobic oxidation of benzyl alcohols. The composite exhibited an excellent catalytic activity and reuse ability of various recycles in air for the aforementioned organic transformations. TEM images of the recovered catalyst showed retained ordered mesostructure of SBA-15 with no damage in the periodic structure of the silicate framework and a good dispersion of in situ generated palladium nanoparticles within the SBA-15 structure.

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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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Ferrocenylimidazolium salts with methylene and phenyl groups bridging the ferrocenyl and alkylimidazolium moieties were synthesized and characterized by spectroscopic and analytical methods. Crystal structures of two new compounds are also reported. Cyclic voltammetry was used to analyze the influence of the two bridging groups or spacers on electrochemical properties of the salts relative to the shifts in the formal electrode or peak potentials (E0 or E1/2) of the ferrocene/ferrocenium redox couple. Results from this study showed that all the salts exhibited higher electrode potentials relative to ferrocene, which is due to the electron-withdrawing effect of the imidazolium ion on the ferrocenyl moiety. Application of the salts as catalysts in transfer hydrogenation of ketones resulted in high conversion of saturated ketones to corresponding alcohols and turnover numbers as high as 1880. The catalysts were chemoselective towards reduction of the C=C bonds of conjugated 3-penten-2-one and 4-hexen-3-one to yield saturated ketones, while unconjugated 5-hexen-2-one was hydrogenated to an unsaturated alcohol. 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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Glassy carbon (GC) and Au electrodes were modified with aminophenyl films by electroreduction of the corresponding diazonium salt. Aminophenyl films were diazotised using both aqueous and non-aqueous conditions, to generate film-based phenyldiazonium ions. The stabilities of the diazonium terminated films, to exposure to air and in acidic solution, were investigated by cyclic voltammetry (CV). For films of the same thickness, those grafted to Au substrates are more stable than those grafted to GC.

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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 synthesis and characterization of pyrazole derivatives of general formula [C6H4-4-R-1-{(3,5-Me2-C3N 2)-CH2-(eta5-C5H4) Fe(eta5-C5H5)}] [R = OMe (1a) or H (1b)] with a ferrocenylmethyl substituent are described.The study of the reactivity of compounds 1 with palladium(II) acetate has allowed the isolation of complexes (mu-AcO)2[Pd{kappa2-C,N-C6H 3-4-R-1-[(3,5-Me2-C3N2)-CH 2-(eta5-C5H4)Fe(eta5-C 5H5)]}]2 (2) [R = OMe (2a) or H (2b)] that contain a bidentate [C(sp2, phenyl), N]- ligand and a central “Pd(mu-AcO)2Pd” unit.Furthermore, treatment of 2 with LiCl produced complexes (mu-Cl)2[Pd{kappa2-C,N-C6H 3-4-R-1-[(3,5-Me2-C3N2)-CH 2-(eta5-C5H4)Fe(eta5- C5H5)]}]2 (3) [R = OMe (3a) or H (3b)] that arise from the replacement of the acetato ligands by the Cl-.Compounds 2 and 3 also react with PPh3 giving the monomeric complexes [Pd{kappa2-C,N-C6H3-4-R-1-[(3,5-Me 2-C3N2)-CH2-(eta5- C5H4)Fe(eta5-C5H 5)]}X(PPh3)] {X- = AcO- and R = OMe (5a) or H (5b) or X- = Cl- and R = OMe (6a) or H (6b)}, where the phosphine is in a cis-arrangement to the metallated carbon atom. Treatment of 3 with thallium(I) acetylacetonate produced [Pd{kappa2-C,N-C6H3-4-R-1-[(3,5-Me 2-C3N2)-CH2-(eta5- C5H4)Fe(eta5-C5H 5)]}(acac)] (7) [R = OMe (7a) or H (7b)]. Electrochemical studies of the free ligands and the cyclopalladated complexes are also reported. The dimeric complexes 3 also react with MeO2C-C{triple bond, long}C-CO2Me (in a 1:4 molar ratio) giving [Pd{(MeO2C-C{double bond, long}C-CO2Me)2C6H3-4-R-1-[(3 ,5-Me2-C3N2)-CH2-(eta 5-C5H4)Fe(eta5-C5H 5)]}Cl] (8) [R = OMe (8a) or H (8b)], which arise from the bis(insertion) of the alkyne into the sigma{Pd-C(sp2, phenyl)} bond of 3.

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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