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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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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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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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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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Chemical engineers work across a number of sectors, processes differ within each of these areas, but chemistry and chemical engineering roles are found throughout, creation and manufacturing process of chemical products and materials. Electric Literature of 12180-80-2. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 12180-80-2, Name is 1,1′-Dibenzoylferrocene

The visible absorption spectra and reduction potentials of 11 ferrocenes containing electron-withdrawing substituents were determined in an N-n-butylpyridinium chloride-aluminum chloride molten salt. When the substituent(s) on the cyclopentadienyl ring(s) of ferrocene were varied, the reduction potential was caused to range over 1.25 V, and the wavelength for maximum absorption of visible light was varied by nearly 200 nm. These changes are greater than have been observed for similar ferrocenes in other nonaqueous solvents. Evidence is presented for specific interactions of particular ferrocenes with the molten salt.

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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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Protein misfolding causes serious biological malfunction, resulting in diseases including Alzheimer’s disease, Parkinson’s disease and cataract. Molecules which inhibit protein misfolding are a promising avenue to explore as therapeutics for the treatment of these diseases. In the present study, thioflavin T fluorescence and transmission electron microscopy experiments demonstrated that hemin prevents amyloid fibril formation of kappa-casein, amyloid beta peptide and alpha-synuclein by blocking beta-sheet structure assembly which is essential in fibril aggregation. Further, inhibition of fibril formation by hemin significantly reduces the cytotoxicity caused by fibrillar amyloid beta peptide in vitro. Interestingly, hemin degrades partially formed amyloid fibrils and prevents further aggregation to mature fibrils. Light scattering assay results revealed that hemin also prevents protein amorphous aggregation of alcohol dehydrogenase, catalase and gammas-crystallin. In summary, hemin is a potent agent which generically stabilises proteins against aggregation, and has potential as a key molecule for the development of therapeutics for protein misfolding diseases.

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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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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 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 label-free method that can doubly image both the physical patterns and the electrochemical information of latent fingerprints (LFPs) on nitrocellulose (NC) membrane has been achieved here by water and scanning electrochemical microscopy (SECM). In this approach, the NC membrane with LFP (LFP/NC) sample was first placed in water, where the different absorption of water onto relatively hydrophobic ridge residues of LFP versus NC membrane background resulted in a high-resolution physical ridge pattern of the fingerprint to naked eyes within just 1?3 s and could further be photographed by a digital camera. Thereafter, the LFP/NC sample was electrochemically imaged by recording the current variations of SECM tip scanning over the label-free fingerprint in the surface-interrogation (SI) mode. The methyl viologen (MV2+) was chosen as the redox mediator to react selectively with the electroactive species in the fingerprint ridge residues rather than furrow regions, which could cause the sharp contrast of the SECM tip current for imaging. Both the collected physical and electrochemical images of LFPs can provide high resolution up to level 2 and level 3 features required for personal identification. In addition, for the first time commercial NC membrane instead of adhesive forensic tape was discovered here for lifting the LFPs from various surfaces, which can then be imaged by this electrochemical approach. Taken together, this method demonstrates a powerful strategy for directly imaging the electrochemical information in LFPs without damaging the fingerprint physical ridge pattern on various substrates, so it has great potentiality in individual identity related applications.

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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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Exclusively planar chirality is exhibited by the ferrocenes obtained in a highly enantioselective synthesis in which a chiral aminoamide acts as a temporary protecting/directing group. This method was used to obtain an enantiomerically pure tetrasubstituted ferrocene, which was transformed into the first C2-symmetric disubstituted ferrocenophane [Eq. (1)].

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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