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The introduction of mechanophores into polymers makes it possible to transduce mechanical forces into chemical reactions that can be used to impart functions such as self-healing, catalytic activity, and mechanochromic response. Here, an example of mechanically induced metal ion release from a polymer is reported. Ferrocene (Fc) was incorporated as an iron ion releasing mechanophore into poly(methyl acrylate)s (PMAs) and polyurethanes (PUs). Sonication triggered the preferential cleavage of the polymers at the Fc units over other bonds, as shown by a kinetic study of the molar mass distribution of the cleaved Fc-containing and Fc-free reference polymers. The released and oxidized iron ions can be detected with KSCN to generate the red-colored [Fe(SCN)n(H2O)6?n)](3?n)+ complex or reacted with K4[Fe(CN)6] to afford Prussian blue.

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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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Standard peptide coupling reactions were use to prepare the N-(ferrocenyl)2 and N-(ferrocenoyl)2 cystine dimethyl ester derivatives 4-11. The ferrocene carboxylic acids 1 and 3 were treated with 1-hydroxybenzotriazole (HOBt), N-(3-dimethylaminopropyl)-N?- ethylcarbodiimide hydrochloride (EDC), l-cystine methyl ester hydrochloride and triethylamine in dichloromethane at 0 C to furnish compounds 4-9. The preparation of compounds 10 and 11 employed the dipeptide derivatives (glycine)2-l-cystine dimethyl ester and (beta-alanine) 2-l-cystine dimethyl ester respectively. The N-(ferrocenyl) 2 and N-(ferrocenoyl)2 cystine dimethyl ester derivatives 4-11, which are potential anion sensing agents, were spectroscopically characterized by a combination of 1H NMR, 13C NMR, IR, UV, DEPT-135 and 1H-13C COSY (HMQC) spectroscopy, mass spectrometry and cyclic voltammetry. The electrochemical detection of dihydrogen phosphate and adenosine nucleotide anions in aqueous electrolyte by monolayers of {N-(ferrocenoyl)-beta-alanine}2-l-cystine dimethyl ester 11 immobilized on gold electrodes using cyclic voltammetry is described. Immobilization of this receptor on a gold electrode surface enabled the recognition process to be detected in aqueous media. The recognition process is as a result of electrostatic interactions between the ferricenium cation and the anion, and hydrogen bonding interactions between the peptide amide bonds and the anion. The complexation process was amperometrically sensed via a reduction in the peak current of the ferrocene/ferricenium redox couple. A linear relationship (R2 = c. 0.99) was observed between anion concentration and change in peak current in both cases.

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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 [(Me2CC5H4)2M]2+ and [(Me(H)CC5H4)2M]2+ dications (M = Ru, Os) were generated and their precursors, dicarbinols, were synthesized. 1H NMR spectral analysis showed that the former dications have a dicarbocation structure. For the [(Me(H)CC5H4)2M]2+ dications, the energies of both the onium and dicarbocation structures are close, and compounds of both types can be simultaneously observed in solution.

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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

 

Why Are Children Getting Addicted To Vinylferrocene

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Product analysis and kinetic data for the reaction of vinylferrocene with thallium triacetate in methanol are reported.Styrene has also been investigated under similar conditions. 1-Ferrocenyl-1,2-dimethoxyethane was the sole product isolated, since the methoxythallation adduct undergoes solvolysis under the reaction conditions. beta-Methylvinylferrocene yields both addition and substitution products in the reaction with Tl(OAc)3, as well as in the previously described reaction with Hg(OAc)2.

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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 hybrid donor?acceptor complexes with a ferrocene moiety and isophorone derivatives were synthesized. Data from 1H NMR, 13C NMR, Fourier transform infrared, atomic absorption and mass spectroscopies and CHN analysis supported the predicted structure of the products. A comparative investigation was performed using UV?visible, cyclic voltammetry and fluorescence measurements. Density functional theory was used to optimize the chromophore structure and calculation of highest occupied and lowest unoccupied molecular orbital energy levels. The ferrocene/isophorone hybrids show useful properties for further development and studies as electro-optic materials.

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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 conformation flexible chemosensor for selective detection of Hg2+ in aqueous media was achieved by incorporating two well-known rhodamine-6G dyes and a ferrocene group within one molecule. Distinguished from the monosubstituted ferrocene derivative which is previously reported a lack of interaction with Hg2+, the title compound was characteristic of two-armed bidendate binding unit. The Hg2+ sensing behavior can be switched via the conformation flexibility. The 1:1 sensor/Hg2+ binding mode was proposed and supported by the titration experiment and ESI mass spectrum. The fluorescent sensor can display a highly selective response of fluorescence enhancement toward Hg2+ and detect the parts per billion (ppb) level of Hg2+ in aqueous environment. Crown 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

 

Discover the magic of the 1,1′-Dibenzoylferrocene

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Lithium tert-alkylperoxyacetylides were reacted with acetyl-, benzoyl, and 1,1?-dibenzoylferrocenes to obtain previously unknown ferrocene-containing acetylenic mono- and diperoxy alcohols. Thermal stability of the products was evaluated.

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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 dual-responsive supramolecular network based on pillar[6]arene-ferrocenium redox-controllable recognition motifs in polymeric backbones is constructed with a ferrocenium-functionalized copolymer and a pillar[6]arene copolymer, in which the first example of pillar[6]arene-functionalized copolymer was synthesized through the reversible addition/fragmentation chain-transfer copolymerization of an acrylate-functionalized pillar[6]arene and methyl acrylate. The resulting supramolecular network exhibits dramatically increased viscosity than the non-cross-linked mixtures and demonstrates a gel-like behavior on macroscale with a transient-network behavior revealed by rheology study. Furthermore, the viscoelastic properties of such supramolecular network can be easily controlled by different external stimuli including redox stimulus and competing host/guest reagents.

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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 simple electrochemical approach was used to evaluate the stability and porosity of titania and silica thin films spin coated on electrode surfaces. This approach involved monitoring the magnitude of the Faradaic current of diffusing redox probes at the modified electrode surfaces over the course of a week to 4.5 months. Relatively nonporous films were examined as well as films templated with polystyrene latex spheres. The results show that templated titania films were significantly more porous compared to non-templated films. After the defect sites in the templated films were blocked, their long-term stability in aqueous electrolyte was evaluated. For titania, blocking was done by spin coating a dilute titania sol on the top of the film whereas for silica, the film was soaked in octyltrimethoxysilane. Both types of titania films (templated and non-templated) were found to be significantly more stable than the corresponding silica films, showing no signs of deterioration in simple electrolyte solutions during the entire evaluation period. In contrast, silica films showed significant deterioration in as little as 3 days. The enhanced stability of the titania films relative to silica films in near neutral electrolyte solutions was attributed to the differences in the point of zero charge of the oxide films.

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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 number of 1,1?-bis(benzo-1,3-dithiol-2-ylidene)ferrocene derivatives 7a-b and 12-14 based on the strong electron donating ability of 1,3-dithiole and ferrocene moieties were synthesized as new pi-donors. The structure and physical properties of these compounds were characterized both by experimental techniques and spectral analysis. These new classes of donor compounds were obtained in very high yields based on modification of the Wittig-Horner reaction and the 1,3-dithiole rings were separated by conjugated spacers including aryl-ferrocenyl- aryl. The electrochemical properties of the new compounds have been studied in comparison to DB-TTF 4 analogues, and the parent ferrocene donor by cyclic voltammetry (CV), using Pt electrode as the working electrode in CH2Cl2 solutions at room temperature. Three subsequent oxidation processes are observed as three oxidation waves associated only with two reduction processes. Polycrystalline samples of 14a-b are conducting sigma rt 14a=0.2 S cm-1 and sigma rt 14b=4.8×10-4 S cm-1) respectively, while compounds 15 and 16 were found essentially as insulator (sigma rt<10-10 S cm-1). The result showed that such a combination of chemo- and biocatalysis improved the catalytic yield more than two times compared with that of sole metal catalysis. We will look forword to the important role of 1271-48-3, and how the biochemistry of the body works.Safety of 1,1′-Ferrocenedicarboxaldehyde

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