Final Thoughts on Chemistry for Ferrocenemethanol

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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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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 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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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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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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An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF3 and nBu4NI has been developed. The trifluoromethylthiolated compounds and alkyl fluorides were selectively formed by changing the ratio of AgSCF3/nBu4NI. This protocol is tolerant of different functional groups and might be applicable to late-stage trifluoromethylthiolation of alcohols.

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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

 

Can You Really Do Chemisty Experiments About 1,1′-Ferrocenedicarboxaldehyde

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Borane, as a DMS or a THF complex, can efficiently reduce a large range of ferrocenyl derivatives (aldehydes, ketones, ethers, acetals, carboxylic acids, esters,…) if they bear at least one oxygen at a carbon at the alpha position. On the contrary, similar molecules, which contain nitrogen instead of oxygen, do not react with borane.

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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 chromatography-free method for desymmetrizing ferrocene is described starting from the readily available dialdehyde. Oxidation of 1,1?-ferrocenedicarboxaldehyde in a water/acetonitrile mixture with KMnO4 produced 1?-formyl-ferrocenecarboxylic acid. The same reaction carried out in a water/acetone mixture produced 1?-[(E)-3-oxo- but-1-enyl]-ferrocenecarboxylic acid.

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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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There is a lot of interest in understanding localized catalytic activities at the micro and nanoscale and designing robust catalysts for photoelectrochemical oxidation of water to address the pressing energy and environmental challenges. Here, we demonstrate that scanning photoelectrochemical microscopy (SPECM) can be effectively employed as a novel technique (i) to modify a photocatalyst surface with an electrocatalyst layer in a matrix fashion and (ii) to monitor its localized activity toward the photoelectrochemical (PEC) water oxidation reaction. The three-dimensional SPECM image clearly shows that the loading of the FeOOH electrocatalyst on the BiVO4 semiconductor surface strongly affects its local PEC reaction activity. The optimal photoelectrodeposition time of FeOOH on the BiVO4 photocatalyst was found to be a?20 min when FeOOH was employed as the electrocatalyst. The electrocatalyst optimization process was conducted on a single photoanode electrode surface, making the optimization process efficient and reliable. The morphology of the formed photocatalyst/electrocatalyst hybrid, inclusive of its localized activity toward the water oxidation reaction, was simultaneously probed. A photoanode surface comprising CuWO4/BiVO4/FeOOH was further prepared in this study and investigated. It was found that the localized photoactivity truly reflects the activity of the local area, differs from region to region, and is contingent on the morphology of the surface. Moreover, the Pt UME is determined as an efficient probe to analyze the photoactivity of the PEC water splitting reaction. This work highlights the novel SPECM technique for enhancement and examination of the catalytic activity of the nanostructured 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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The present invention relates to tricyclic compounds of formula (I) or pharmaceutically acceptable salt thereof as mPGES-1 inhibitors. These compounds are inhibitors of the microsomal prostaglandin E synthase-1 (mPGES-1) enzyme and are therefore useful in the treatment of pain and/or inflammation from a variety of diseases or conditions, such as asthama, osteoarthritis, rheumatoid arthritis, acute or chronic pain and neurodegenerative diseases. (I)

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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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Acetyl ferrocene and diacetyl ferrocene both readily react with an excess of hydrazine to afford the corresponding hydrazone compounds. These compounds can then be linked to Re(CO)3 via a metal-mediated Schiff base reaction, resulting in a series of ferrocene-Re(CO)3 conjugates with different stoichiometries. Conjugates with 1:1, 1:2, and 2:1 ferrocene: Re(CO)3 ratios can be produced via this “modular” type synthesis approach. Several examples of these conjugates were structurally characterized, and their spectroscopic, electrochemical, and spectroelectrochemical behaviors were investigated. The electronic structures of these compounds were also probed using DFT and TDDFT calculations.

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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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Diabetes is a group of heterogeneous disorders with the common elements of hyperglycemia and glucose intolerance because of insulin deficiency, impaired effectiveness of insulin action or both. The best marker for long-term glycemic control is whole-blood glycated hemoglobin (HbA1c), since its levels correspond to the long-term progression of diabetes without short-term fluctuations in the behavior of glucose. Currently, common laboratory methods to recognize glycated proteins are high-performance liquid chromatography, immunoassay and electrophoresis. The accuracy and the precision of A1C assays at least match those of glucose assays. Consequently, the International Expert Committee (with members appointed by the American Diabetes Association, the European Association for the Study of Diabetes, and the International Diabetes Federation) decided that the A1c assay should be recognized as the primary method for diagnosing diabetes. In this review, we look at electrochemical biosensors for the detection of glycated proteins developed in recent years.

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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