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In situ scanning electrochemical microscopy (SECM) and scanning tunneling microscopy (STM) assisted scanning reference electrode technique (SRET) were applied for the first time to study the interaction of thiosulfate with Alloy 800 surfaces in aqueous chloride solutions. Electrochemical impedance spectroscopy (EIS) and scanning electron microscope (SEM) were also performed to understand the interaction mechanism. The results showed that the effect of 0.075 mol/L thiosulfate in 0.6 mol/L chloride solutions strongly depended on the potential. There was no aggressive effect at the corrosion potential where the passive layer was intact, but a combined effect was observed with the presence of chloride ions at high potential where the passive layer was broken down.

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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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Hydroalumination reaction was effectively carried out on ferrocenylnitrile in the synthesis of imidoalane cluster [HAlNCH2C5H 4FeCp]6 (3). Compound 3 exhibits a reversible electrochemical behavior. In the presence of ferrocenylmethanol, meta thesis reactions were carried out on [HAlNCH2(C4H 3S)]6 (4) and [HAlNCH2Ph]6 (5) in the synthesis of [CpFeC5H4CH2OAlNCH 2(C4H3S)]6 (6) and [CpFeC 5H4CH2OAlNCH2Ph]6 (7). The ferrocenylmethoxide groups present in these two compounds show a single reversible oxidation wave, which suggests their electrochemical equivalence. Electrochemical studies were also carried out on the carbaalane [(AlH) 2(FcCCAl)4(AlNMe3)2(CCH 2Ph)6] (9), which exhibited a considerably broadened wave with shoulders preceding the main anodic and cathodic peak, and it can be assigned to weak electronic interactions between the individual ferrocenyl sites.

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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 reactivity of ferrocene derivatives with respect to p-quinones in acid media has been studied. A tentative mechanism of oxidation of ferrocene with p-qionone in acid media including two-step reduction of p-quinone to hydroquinone is proposed.

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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 ferrocene-based compartmental ligand, H2L, was synthesized by the reaction of diacetyl ferrocene with hydrazine hydrate followed by a condensation reaction with o-vanillin. [L]2- possesses a dual coordination pocket, an inner pocket of 2 imino nitrogens and two phenolate oxygens and an outer pocket of two phenolate and two methoxy oxygen atoms. Utilizing this ligand, several ZnII/LnIII heterobimetallic complexes were assembled: [LZn(mu-OAc)Dy(NO3)2] (2), [LZn(mu-OAc)Tb(NO3)2] (3), [LZn(mu-OAc)Gd(NO 3)2·2CHCl3] (4), [LZn(mu-OAc) Er(NO3)2] (5), [LZn(mu-OAc)Ho(NO3) 2] (6), [LZn(mu-OAc)Eu(NO3)2] (7). All of these metal complexes are neutral and isostructural: the ZnII ion occupies the inner coordination pocket while the LnIII ion occupies the outer coordination pocket of the doubly deprotonated ligand [L] 2-. Zn(ii) has a coordination number of 5 (2N, 3O) in a square pyramidal coordination geometry while Ln(iii) has a coordination number of 9 (9O) in a distorted tricapped trigonal prismatic geometry. Zn(ii) and the 4f metal ion are bridged to each other by two phenolate oxygen atoms and an acetate ligand. ESI-MS reveals that 2-7 retain their structural integrity in solution. Cyclic voltammetry of 1-7 revealed a quasi-reversible oxidation (involving the ferrocene motif) and an irreversible reduction of the hydrazone unit. Magnetic studies of 2, 3 and 6 were carried out. Ac susceptibility studies did not reveal slow relaxation of magnetization.

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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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Kinetically stabilized 1,1′-bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallo-graphic analyses. The electronic structures of the 1,1′-bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic vol-tammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1′-bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1′-bis[(Z)-diphosphenyl]ferrocene group 6 metal tetracarbonyl complexes, [M(CO) 4{(Z,Z)-(BbtP=PC 5H4)2Fe}] (M = Cr, Mo, and W). The molecular structures of these complexes were determined by spectroscopic analyses ( 1H, 13C, and 31PNMR spectra, and UV-vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d? pi*p=p electron transitions due to the iron and group 6 metals were detected by using UV-vis spectroscopy, and these results were supported by theoretical calculations.

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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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Treatment of 1,1?-diacetylferrocene (10) with excess piperidine and a stoichiometric amount of TiCl4 in pentane leads to CC-coupling of the two functional groups at the ferrocene framework. This enamine condensation reaction leads to the formation of the 1,3-connected dienamine-bridged [3]ferrocenophane system 13a. Complex 13a was characterised by X-ray crystal structure analysis. The analogous TiCl4-mediated coupling and condensation reactions of 10 with morpholine, pyrrolidine or methyl-isopropylamine yield the corresponding substituted [3]ferrocenophane systems 13b-d.

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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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New, thermally stable dipolar ferrocene-diketopyrrolopyrrole (Fc-DPP) dyads with alkene as a linker exhibited structure dependent first hyperpolarizabilities, betaHRS, recorded by a femtosecond HRS technique using a femtosecond (120 fs) pulsed laser light system at 900 nm at ambient temperature. On the basis of linear optical, electrochemical and TD-DFT studies, a good structure-polarization relationship has been established to account for the observed trends in first hyperpolarizabilities. The dyads exhibited fluctuating but matching solvatochromism. Nonlinear optical properties are modulated both by the strength of the acceptor as well as the length and nature of the pi-conjugation bridge. betaHRS of the dyads were compared with structurally related dyads in which the DPP core and the Fc donor are linked via an alkyne bridge. It is interesting to observe that the replacement of an alkyne link with alkene in these D-pi-A chromophores does not necessarily furnish enhanced betaHRS.

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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 class of novel, easily accessible and air-stable 1-[bis(trifluoromethyl) phosphine]-1′-oxazolinylferrocene ligands has been synthesized from ferrocene. It became apparent that these ligands can be used in the regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates in a highly efficient manner. Excellent regio- and enantioselectivity could be obtained for a wide range of substrates.

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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 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