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A study has been made of the possibility of increasing the stability of the 1,1?-bis(diphenylphosphino)ferrocenium monocation by introduction of appropriate substituents into the cyclopentadienyl ligands. The electrochemical behaviour of a series of 1,1?-bis(diphenylphosphino)ferrocenes bearing substituents with a range of electronic properties has been examined. The results reveal that, the higher the electron-donating ability of the substituents, the longer is the lifetime of the corresponding 1,1?-bis(diphenylphosphino)ferrocenium monocation. However, no stable ferrocenium cation has been obtained; mass spectrometry shows that mixtures of mono- and di-bis(diphenylphosphine)oxides are ultimately formed as products resulting from decomposition of the initially electrogenerated 1,1?-bis(diphenylphosphino)ferrocenium species.

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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 method for the hydrosilylation of alkynes controlled by a platinum catalyst with a monophosphine ligand (called TBSO-MOP) was explored. The platinum-catalyzed multicomponent and sequential silylation reaction involving alkynes, alcohols, and dihydrosilanes resulted in the highly stereoselective and high-yielding construction of functional (E)-vinylsilyl ethers. Moreover, the one-pot bis-hydrosilylation of terminal alkynes with dihydrosilanes was also achieved with the same platinum catalyst 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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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 ferrocene naphthyridine derivatives were successfully synthesized. The di-substituted ferrocene derivative FecDN behaves as a selective visual chemosensor for mercury ions, exhibiting a rapid and clearly visible precipitation with good selectivity (precipitation) and sensitivity (0.01 muM). The interaction of the ferrocene derivatives and metal ions was investigated by ultraviolet-visible spectroscopy (UV-vis), electrochemical methods, 1H NMR, as well as infrared (IR), and energy dispersive X-ray spectroscopy (EDX). The application of FecDN in the detection and removal of mercury ions is very simple, rapid, and intuitive.

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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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4-Thiaflavan is a sulfur-substituted flavonoid with a benzoxathiin scaffold. The aim of this work is to compare abilities of sulfur and oxygen atom, hydroxyl groups, and ferrocene moiety at different positions of 4-thiaflavan to trap radicals and to inhibit DNA oxidation. It is found that abilities of thiaflavans to trap radicals and to inhibit DNA oxidation are increased in the presence of ferrocene moiety and are further improved by the electron-donating group attaching to thiaflavan skeleton. It can be concluded that the ferrocene moiety plays the major role for thiaflavans to be antioxidants even in the absence of phenolic hydroxyl groups. On the other hand, the antioxidant effectiveness of phenolic hydroxyl groups in thiaflavans can be improved by the electron-donating group. The influences of sulfur and oxygen atoms in thiaflavans on the antioxidant property of para-hydroxyl group exhibit different manners when the thiaflavans are used to trap radicals and to inhibit DNA oxidation.

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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 tetramethylene-bridged PMes2/B(C6F 5)2 frustrated Lewis pair (FLP) 8 was prepared by hydroboration of Mes2P-(CH2)2CH=CH2 with HB(C6F5)2. It is an active FLP that splits dihydrogen under mild conditions and, consequently, serves as a metal-free hydrogenation catalyst for a variety of substrates. It also reacts typically with terminal acetylenes. The C4-bridged FLP 23 was prepared by HB(C6F5)2 hydroboration of 1- dimesitylphosphino-2-vinylferrocene. It represents a rare example of a FLP where the equilibrium between the open form and the closed internal P/B adduct form is experimentally observable. It also shows a variety of typical FLP reactions, including dihydrogen splitting. The FLPs 8 and 23 (open form) and many precursors and products were characterized by X-ray diffraction.

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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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For the first time a novel, simple and facile approach is described to construct highly stable glucose oxidase (GOx) multilayer onto glassy carbon (GC) electrode using thiourea (TU) as a covalent attachment cross-linker. The layer by layer (LBL) attachment process was confirmed by cyclic voltammetry, electrochemical impedance spectroscopy and Fourier transform infrared reflection spectroscopy (FT-IR-RS) techniques. Immobilized GOx shows excellent electrocatalytic activity toward glucose oxidation using ferrocenemethanol as artificial electron transfer mediator and biosensor response was directly correlated to the number of bilayers. The surface coverage of active GOx per bilayer, heterogeneous electron transfer rate constant (ks) and Michaelis-Menten constant (KM), of immobilized GOx were 1.50 × 10-12 mol cm-2, 9.2 ± 0.5 s-1 and 3.42(±0.2) mM, respectively. The biosensor constructed with four-bilayers of TU/GOx showed good stability, high reproducibility, long life-time, fast amperometric response (5 s) with the high sensitivity of 5.73 muA mM -1 cm-2 and low detection limit of 6 muM at concentration range up to 5.5 mM.

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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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New tetrakis-and hexakis(1H-pyrrole-2-carbaldehyde) anion receptors are described. The anion binding properties of these receptors were studied in organic media and in the solid state. The receptors displayed good affinity for the dihydrogenphosphate and pyrophosphate anions (as the tetrabutylammonium salts) in chloroform even in the presence of a polar protic solvent, methanol. Solution phase spectroscopic analyses proved consistent with the binding mode seen in single crystal structural studies of the dihydrogenphosphate and pyrophosphate complexes and provided support for the contention that these receptors undergo conformational reorganization in order to accommodate the bound oxoanions both in chloroform solution and in the solid state.

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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 reaction of tris(3-iodopentane-2,4-dionato)cobalt(III) with vinylferrocene in the presence of triphenylphosphine and a catalytic amount of PdII produced two structural isomers.The characterisation of these isomers, 2- and 3-ferrocenyl-4-acetyl-2,3-dihydro-5-methylfuran <(B) and (C), respectively> is described.Their structures have been determined by single-crystal X-ray diffractometry: (B) is orthorhombic, space group Pbca with a=9.821(2), b=10.414(4), c=27.761(6) Angstroem, final R=0.031, R’=0.050 for 1706 reflections; (C) is monoclinic, space group is P21/c with a=9.692(1), b=7.678(5), c=19.082(3) Angstroem, final R=0.031, R’=0.048 for 1641 reflections.

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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 inhibitive effects of alternating current-treated (AC-treated) mixed self-assembled monolayer (SAMHL/DT) with 2-(Pyridin-2-yliminomethyl)-phenol (HL) and dodecanethiol (DT) on copper corrosion have been studied by using the scanning electrochemical microscope (SECM) combined with Tafel and electrochemical impedance spectroscopy (EIS) methods When the AC-treated potential is applied in the cathodic region, the inhibition efficiency increases, and the pitting dynamic processes are inhibited. All the results reveal that the AC-treated effects are related to both the formation of complex compounds and the reduction of the oxide film on the surface of copper.

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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