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The preparation and characterization of a series of dyads containing ferrocene donor and naphthalimide acceptor units, separated by aromatic spacer groups, are reported. The compounds contain a ferrocene-ethenyl spacer component linked to the 4-position of a naphthalimide by an ethynyl bridge, Fc-CH=CH-spacer-C?C-naphthalimide (Fc = ferrocenyl), where the spacers are 1,4-phenyl, 4,4?-biphenyl, and 9,10-anthryl. Precursors to the dyad systems, halo-spacer-C?C-naphthalimide, are also characterized where the halo-spacers are 1-bromophenyl, 4-bromobiphenyl, and 9-iodoanthryl. Various synthetic strategies are examined, with attachment of the spacer to 4-ethynylnaphthalimide followed by reaction with ethenylferrocene proving the most effective route. Crystal structures of the donor-spacer-acceptor (D-S-A) compound (E)-1-ethenylferrocenyl-4-(4-ethynyl-N-methyl-1,8-naphthalimide)benzene (7) and the precursor compounds (E)-4-bromo-4?-(ethenylferrocenyl) biphenyl (2) and 4-ethynyl-4?-(4-ethynyl-N-methyl-1,8-naphthalimide) biphenyl (4) are reported, with packing in the two naphthalimide derivatives dominated by offset pi-stacking interactions. Compounds containing the ferrocenyl groups show the anticipated one-electron oxidation processes at potentials that vary little with the spacer groups. Both the ferrocenyl derivatives and their naphthalimide precursors show reversible reduction waves. The single wave for the phenyl and biphenyl compounds and their precursors is assigned to reversible one-electron reduction of the naphthalimide unit. The corresponding anthracene derivatives display two reversible reductions associated with the naphthalimide and the anthryl moieties, respectively.

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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 new method for substitution of a vinylic hydrogen with an alkyl group (a Mizoroki-Heck type transformation) was developed by a titanocene catalyst in the presence of nBuMgCl. This reaction could proceed regio- and stereoselectively under mild conditions to afford E-olefins using primary and secondary alkyl halides. The reactions of aliphatic alkenes, e.g., 1-octene and internal alkenes, were sluggish. When t-alkyl halides were employed, alkylative dimerization of alkenes proceeded exclusively to give symmetrical vic-diarylalkanes. These reactions involved addition of alkyl radicals to arylalkenes to form benzyl radicals as a carbon-carbon bond-forming step. Dimerization of thus formed benzyl radicals afforded symmetrical alkanes and beta-hydrogen elimination from benzyltitanocene intermediates gave alkylated alkenes. A possibility that titanocene activates alkenes as radical accepters was also 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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Different modes of scanning electrochemical mapping (SECM) such as surface generation/tip collection (SG/TC), amperometry, AC-SECM and potentiometry were employed to characterize the active/passive domains, hydrogen gas (H2) evolution and local pH on a corroding surface of AZ31 in simulated biological fluid (SBF). It was found that the main domains of H2 evolution are associated with lower insulating properties of the surface as well as higher local pH. The near surface pH was found to be highly alkaline indicating that, even in a buffered solution such as SBF, the local pH on a corroding AZ31 surface can be significantly different to the bulk pH.

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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 synthesized poly(epichlorohydrin-co-2-(methoxy)methyl oxirane) [poly(ECH-co-MOMO)] and ferrocene modified poly(epichlorohydrin-co-2-(methoxy) methyl oxirane) [poly(FECH-co-MOMO)] based polyurethane networks. The polyurethane networks were prepared from prepolymer diol, 1,6- hexamethylenediisocyanate (HDI), and HDI-trimer with an [NCO]/[OH] ratio of 1.05 and an [isocyanate trimer]/[total NCO] ratio of 0.3 followed by accelerated aging at 80 C for 72 h. Thermal decomposition kinetics of urethane networks were investigated by thermal gravimetric analysis (TGA). Both the iso-conversional and Vyazovkin methods were used to investigate the thermal decomposition behavior for evaluating kinetic parameter of poly(ECH-co-MOMO) and poly(FECH-co-MOMO) based polyurethane networks. The decomposition temperature of the poly(ECH-co-MOMO) based polyurethane network was lower than that of the poly(FECH-co-MOMO) based polyurethane network. From the Vyazovkin method, the maximum activation energies of poly(ECH-co-MOMO) and poly(FECH-co-MOMO) based polyurethane networks were 220 kJ/mol and 240 kJ/mol, respectively.

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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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57Fe NMR spectra of 20 ferrocene derivatives with natural abundance of 57Fe have been recorded by the conventional pulse Fourier transform technique using ferrocene as internal standard for the chemical shifts.Shift contributions of the substituents are discussed qualitatively.

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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 new dismountable and reusable microchip for electrophoretic separation coupled to amperometric detection was developed. For this purpose, a new home made three-microbands electrode system was developed and microfabricated based on screen-printing for the inclusion of graphite/polydimethylsiloxane (C-PDMS) composite in microchannels down to 30 mum width. The composition of the composite as well as the fabrication methodology were optimized for an easy handling and an optimized electrochemical behavior. The electrochemical characterization of this composite material was first performed in bulk format (disc-shaped electrode, 6 mm diameter). It was then transposed to the micrometric scale for its integration in an original glass-NOA81-PDMS microfluidic device allowing for reversible sealing. The microband electrodes were characterized by scanning electron microcopy and cyclic voltammetry, illustrating a good control of the microelectrode width. Then, the analytical performances of the C-PDMS composite microelectrodes were evaluated using Ru(NH3)6 3+ and FcMeOH as model electroactive molecules. The electrophoretic separation and quantitation of Ru(NH3)6 3+ were then performed in a background electrolyte made of hydrochloric acid and sodium chloride, leading to a LOD and a LOQ of 3.4 mumol L?1 and 11.3 mumol L?1, respectively. The re-openable NOA-based microdevice permits to regenerate the electrode surface by simply repositioning the microband on a new spot, allowing for robust analysis in a reusable system.

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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 easy functionalization of tags and solid supports with the vinyl sulfone function is a valuable tool in omic sciences that allows their coupling with the amine and thiol groups present in the proteogenic residues of proteins, in mild and green conditions compatible with their biological function.

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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 present review emphasizes on the quantification of biogenic amines (BAs) which are regarded as a quality indicator of food freshness or spoilage and for evaluating microbial action while food processing. BAs have various potential adverse effects on human health and they are widely found in varying concentrations in different food stuffs. In the quest for a reliable method for their precise detection, BA biosensors have emerged as an efficient tool which enables rapid and accurate assessment in miniature form. Various combinations of amine oxidase enzymes have been used for the fabrication of biosensors in order to enhance specific biorecognition and signal transduction. This article also summarizes the widely employed components used in the construction of a pertinent biosensor and the research results conducted previously. The meticulous description regarding the choice of transducers and the significant role of mediators in a high response biosensor has been reviewed. Moreover, it also encompasses the utilization of highly attractive electrolytic characteristics of nanoparticles to enhance the specificity and accuracy of BA biosensors.

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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 heterobimetallics containing ferrocene and Pd(II) or Pt(II) have been synthesized by oxidative addition of ferrocene-substituted halothiophenes with zerovalent palladium or platinum precursors. The stable solids were thoroughly characterized by elemental analysis, NMR, UV-vis spectroscopy, and cyclic voltammetry. The rich redox chemistry of the complexes depends on the conjugation length that separates the two metal sites. The crystal structure of a platinum sigma-thienyl complex, (C5H5)Fe(C5H4CH=CH-th-Pt(PPh 3)2(Br)) (th = 2,5-disubstituted thiophene) has been determined.

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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