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The preparation of ferrocenylmethyl azide and its use as a synthetic intermediate is discussed. Acid catalyzed decomposition of the azide provides the novel product bis(ferrocenylmethyl)amine.

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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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A series of several new families of ferrocene-containing imidazolium salts were synthesized by etherification of ferrocene methanol, acylation of ferrocene, and amide coupling of ferrocene carboxylic acid. The etherification was achieved by an acid-catalyzed procedure and very good yields of between 86-93-% were obtained. Next to the nature of the linkage itself, the lengths of the alkyl chains linking the ferrocenyl moiety and the imidazolium group and the nature of the counterions were also varied. Interestingly, a gamma-effect can be observed for the ether compounds but this effect was only visible in 13C NMR spectroscopy. These new redox-active ionic liquids were fully characterized by FTIR, 1H, 19F, and 13C NMR spectroscopy, and by MS, HRMS and elemental analysis. A novel series of ferrocenated ionic liquids with different spacer species between the ferrocenyl moiety and the imidazolium group have been developed. The spacer units have been established by amide coupling, etherification and acylation. The latter reaction is strongly influenced by the chain length of the acid chloride and a gamma-effect is observable for the ether compounds. Copyright

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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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Scanning electrochemical microscopy represents a powerful tool for electro(chemical) characterization of surfaces, but its applicability has been limited in most cases at microscale spatial resolution, and the greatest challenge has been the scaling down to the nanoscale for fabrication and the use of nanometer-sized tips. Here, Pt nanoelectrodes with nanometer electroactive area were fabricated and employed for imaging a distribution of gold nanoparticles (AuNPs) and bioelectrocatalytic activity of a redox-active enzyme immobilized on gold surfaces. [Figure not available: see fulltext.].

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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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We have prepared a novel 3D porous biomaterial combining poly (dl-lactic acid) (PDLLA) and graphene and multi-walled carbon nanotubes oxides (MWCNTO-GO) composite. PDLLA as control and a high loading of PDLLA/MWCNTO-GO (50/50 w/w) bioscaffolds were prepared and functionalized. MWCNTs were exfoliated to form MWCNTO-GO by oxygen plasma etching. The later was also applied to enhance the scaffolds wettability, attaching oxygen-containing groups on their surfaces. This approach produced a porous architecture observed by scanning electron microscopy and semi-quantified by electrochemical analysis. The later also indicated a notable increase on the conductivity of PDLLA/MWCNTO-GO scaffold compared to MWCNTO-GO free PDLLA (about 5 orders of magnitudes at low frequencies). Thermogravimetric analysis showed that the MWCNTO-GO acted protecting the PDLLA matrix, enhancing its thermal stability. The PDLLA/MWCNTO-GO scaffolds had significant cellular adhesion, did not present cytotoxicity effect, besides reduced bactericidal proliferation and produced mineralized tissues in SBF media. The metallic MWCNTO-GO powder held together by PDLLA polymer opens a whole new branch of applications, including bioelectroanalyses, drug delivery systems and tissue engineering.

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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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The emergence of nanoscience and nanotechnology has opened up new horizons to researchers. In this regard, carbon nanomaterials are considered as the cornerstone of numerous investigations. Among various carbon nanostructures, ?Carbon nanoparticles (CNPs)? have attracted a great deal of attention during the past few years due to their unique properties such as high surface area, non-toxicity, biocompatibility as well as simple and low-cost synthetic procedures via environmentally friendly routes. Thanks to these properties along with their interesting optical behavior, CNPs have found diverse applications in the fields of bioimaging, nanomedicine, photo/electro-catalysis, and bio/chemical sensing. Moreover, their fascinating electrochemical properties including high effective surface area, excellent electrical conductivity, electrocatalytic activity as well as high porosity and adsorption capability, turn them to potential candidate for electrochemical purposes particularly sensing. The recent article, comprehensively reviews the usage of CNPs in design and construction of electrochemical sensors. It starts with a brief introduction of their properties and synthesis methods, then presents the electrode modification procedures, and finally come up with an overview of the proposed electrochemical sensing platforms based on CNPs. We hope that the recent review article will illuminate new lights in the minds of researchers active in this area and incorporates to promote the activities in this field of research.

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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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The kinetics of the oxygen reduction reaction (ORR) at carbon-supported transition-metal oxides in alkaline solutions is systematically investigated as a function of the nature of the B-site. The study is focused on LaBO3 (B=Cr, Co, Fe, Mn and Ni) nanoparticles synthesized by using an ionic-liquid route, offering fine control over phase purity and composition. Activity towards the ORR was compared with the commercial Pt/Etek catalyst. Detailed electrochemical analysis employing a rotating ring-disk electrode provides conclusive evidence that the carbon support plays an important contribution in the faradaic responses. Decoupling the contribution of the carbon support uncovers that the reactivity of LaMnO3 towards the four-electron ORR pathway is orders of magnitude higher than that for the other lanthanides. We rationalize these observations in terms of changes in the redox state at the B-site close to the formal oxygen reduction potential.

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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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Facile synthetic procedures to synthesize a series of difficult-To-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(n5-C5H5)(n5-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group Pi. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 < Epa < 76 mV versus FcH/FcH+ involves exclusively an Fe(II) to Fe(III) process. Further DFT calculations showed this one-electron oxidation is followed by proton loss on the thiol group to generate a radical, Fc(CH2)nS, with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S- (CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group E = Epa,monomer - Epc,dimer ? 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. 1H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-Assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, deltaE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-Thioether, Fc(CH)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au. I am very proud of our efforts over the past few months, and hope to 1273-94-5 help many people in the next few years. .Synthetic Route of 1273-86-5

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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CAN-catalyzed reactions between alpha-ferrocenyl ethanol or ferrocenyl methanol and S-, N- and O-carborane nucleophiles are reported. This approach is an efficient and simple procedure for the preparation of carborane derivatives containing ferrocenyl units. Energy and geometry optimizations of some carboranylthio-, carboranylamino- and carboranyloxy-substituted ferrocenes have been calculated using the density functional theory. A series of new ferrocene-containing carborane 1,2,3-triazoles have been synthesized in good yields through a facile copper-mediated 1,3-dipolar cycloaddition reactions of alkynyl ferrocenes with [(o-carboran-1-yl)methyl]azide. Molecular structure of carborane-substituted ferrocenyl triazole was established by single crystal X-ray diffraction study. Representative examples of all ferrocenyl carboranes prepared were characterized by IR, 1H and 11B NMR spectroscopy.

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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 behaviour of three ZrTi alloys (Zr5Ti, Zr25Ti and Zr45Ti) in Ringer’s solution has been investigated. Their resistance against localized corrosion has been determined from cyclic potentiodynamic polarization (CCP) and electrochemical impedance spectroscopy (EIS) measurements, whereas scanning electrochemical microscopy (SECM) was applied to investigate the local reactivity of the passive films developed on the materials, and scanning electron microscopy (SEM) was employed to characterize the surface morphology of the alloys subjected to anodic polarization. An increased reactivity could be detected with SECM when the metal samples were polarized at +0.50 V SHE, though the extent of this feature greatly depended on the nature of the metallic material. In addition, At 37 C, the Zr5Ti alloy was susceptible to localized corrosion. Though Zr25Ti alloy presented rather low pitting potential, the spontaneous corrosion potential of the material was sufficiently negative to require overpotentials around 600 mV for breakdown to occur. Finally, the Zr45Ti alloy exhibited a larger passive range in the polarization curve, and it was resistant to localized corrosion.

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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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Features of the oxidation of hydroxymethylferrocene with molecular oxygen in organic solvent in the presence of weak and strong Broensted acids were studied. The resulting data were compared with published data on ferrocene and hydroxyferrocene oxidation, which made it possible to assess the trend in the oxidation mechanism in going from ferrocene pi complexes to their hydroxyferrocene and hydroxymethylferrocene analogs. A conclusion was drawn that each of the ferrocenes reacts with oxygen in quite a specific way.

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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