Top Picks: new discover of Vinylferrocene

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The redox switching of poly(vinylferrocene) (PVF) films was investigated using the electrochemical quartz crystal microbalance in conjunction with cyclic voltammetry (at different voltage scan rates) and reverse potential steps. The mechanism of the redox process was determined using PVF films supported on Au electrodes and exposed to aqueous bathing solutions of 0.1 M sodium hexafluorophosphate. PVF electro-oxidation proceeds via coupled oxidation of uncharged ferrocene sites and entry of counterion and is followed by the entry of water into the film. Structural changes within the polymer may also accompany the latter two steps. Any of these three steps may be the slowest for particular redox conditions. The controlling kinetic step depends on the film’s instantaneous water content, its instantaneous oxidation state, the electrochemical control function, the direction of redox switching, and the associated time scale of the experiment. We describe a new general quantitative approach based upon comparison of the instantaneous fluxes of solvent (water) and counterion during the redox cycle to characterize the rate-controlling process as a function of the extent of film oxidation. This new methodology has the capability to resolve time scale- and potential- (charge-) dependent mechanistic shifts and film relaxation phenomena as they are reflected through the ratio of fluxes of solvent and counterions.

Use of the flux ratio method for mechanistic diagnosis in electroactive polymer film redox switching

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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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Difluoroethylsulfonium salt, Ph2S+CH2CF2H OTf?, was developed into a convenient difluoromethylcarbene reagent for the iron-catalyzed cyclopropanation of terminal olefins, giving various difluoromethyl-cyclopropanes with excellent diastereoselectivities and in high yields.

Difluoromethylcarbene for iron-catalyzed cyclopropanation

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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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[1.1.1]Propellane is a highly strained tricyclic hydrocarbon whose reactivity is dominated by addition reactions across the central inverted bond to provide bicyclo[1.1.1]pentane derivatives. These reactions proceed under both radical and two-electron pathways, hence, providing access to a diverse array of products. Conversely, transition metal-catalyzed reactions of [1.1.1]propellane are underdeveloped and lack synthetic utility, with reported examples generally yielding mixtures of ring-opened structural isomers, dimers, and trimers, often with poor selectivity. Herein, we report that nickel(0) catalysis enables the use of [1.1.1]propellane as a carbene precursor in cyclopropanations of a range of functionalized alkenes to give methylenespiro[2.3]hexane products. Computational studies provide support for initial formation of a Ni(0)-[1.1.1]propellane complex followed by concerted double C-C bond activation to give the key 3-methylenecyclobutylidene-nickel intermediate.

Methylenespiro[2.3]hexanes via Nickel-Catalyzed Cyclopropanations with [1.1.1]Propellane

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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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Application In Synthesis of Vinylferrocene. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1271-51-8, Name is Vinylferrocene

Pd(OAc)2-catalyzed Sonogashira coupling reactions of alkynes and a variety of aryl halides with 1,3-bis(5-ferrocenylisoxazoline-3-yl)benzene as an efficient non-phosphorus ligand under copper-free conditions are presented. The main advantages over previous methodologies include low catalyst loading (0.2 mol% Pd(OAc)2 and 0.4 mol% ferrocenyl bisoxazoline ligand are sufficient for these coupling reactions), less problematic reaction medium (water?dimethylformamide) and more convenient operation (no requirement for nitrogen protection).

Ferrocenyl bisoxazoline as an efficient non-phosphorus ligand for palladium-catalyzed copper-free Sonogashira reaction in aqueous solution

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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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Two novel isoxazoline N,N-bidentate ligands with ferrocene backbone have been synthesized and employed for the palladium-catalyzed Heck coupling reaction. Among them, 1,3-bis-(5-ferrocenylisoxazoline-3-yl)benzene was found to be thermally stable and a highly effective ligand for Heck coupling reaction in neat water without N2 protection, affording the desired coupling products in good to excellent yield with high diastereoselectivity. The developed catalytic system was also well workable for 1,2-disubstituted alkenes, which were less involved in the Heck reaction for its larger steric hindrance. Copyright

Novel isoxazoline ligand with ferrocene backbone: Preparation and application in Heck reaction with water as solvent

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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 [(PCy3)2Cl2Ru=CH-Ph] (I) with vinylferrocene 1 and 1-ferrocenyl-1,3-butadiene 2 yielded solid products. These new complexes were characterized by 1H NMR, 31P NMR and 13C NMR spectroscopy. X-ray crystal structures of both the complexes have been solved. The crystal structure of II confirmed the assigned structure and revealed existence of two sets of intermolecular C-H-Cl(M) type interactions, viz. (Ru)Cl-H-C(ferrocene) and (Ru)Cl-H-CHCl2. The air-stable, dark solid II is an efficient catalyst for ring-opening metathesis polymerization (ROMP) of cyclopentene, norbornene and cycloocta-1,5-diene. Electrochemical behavior of the complexes clearly reflects electronic communication between two metal centers.

Synthesis, structure, electrochemistry and ROMP-activity of new ferrocenyl analog of Grubbs’ metathesis catalyst

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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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Chemistry is a science major with cience and engineering. The main research directions are preparation and modification of special coatings, and research on the structure and performance of functional materials. In a patent, 1271-51-8, name is Vinylferrocene, introducing its new discovery. Formula: C12H3Fe

A combination of electrochemical and radiotracer methods offers a unique possibility of studying the motion of counter- and co-ions during electrochemical transformations occurring in a polymer film. In addition, information can be obtained about the embedding of electrolytes during electropolymerization penetration of electrolytes into the films prepared by solvent-evaporation procedures, the ion-exchange behavior, and the mechanism of the redox processes. Results on poly/vinyl ferrocene/tetracyanoquinodimethane polyester, polypyrrole, and polyaniline are described.

Combined electrochemical and radiotracer study on the ionic charge transport coupled to electron transfer and ionic equilibria in electroactive polymer films on electrodes

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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 result showed that such a combination of chemo- and biocatalysis improved the catalytic yield more than two times compared with that of sole metal catalysis. We will look forword to the important role of 1271-51-8, and how the biochemistry of the body works.Application of 1271-51-8

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New ferrocenyl-subtituted compounds containing two different central cores (isocyanurate and 1,3,5-phenylene) and extended by two kinds of branches bearing both vinyl ferrocenyl (1 and 3) and cross-conjugated ferrocenyl-chalcone (2, 4 and 5) as endgroups have been synthetized and characterized both spectroscopically and electrochemically. These molecules have been synthesized in order to investigate the electronic properties imparted by both types of branches when they are connected to the central core. For all compounds, electrochemical studies have showed a simultaneous oxidation of all ferrocene units present in each compound. For all of them, except for compound 2, a chemically reversible oxidation wave on the voltammograms has been observed. In contrast, for compound 2, a chemically irreversible oxidation wave is obtained. Moreover, the vinyl ferrocenyl derivatives have presented a lower redox peak potential with respect to ferrocene standard compound, and the ferrocenyl-chalcone bearing derivatives, in accordance with a change in the electron releasing capability of these endgroups, have been oxidized at a higher potential. Bathochromic shifts of the active transitions in Uv-Vis region have been observed, which are associated to the presence of carbonyl groups in those molecular structures containing it. These results are in agreement with theoretically calculated transition energies, which have been obtained for compounds 1 and 2 using Time Dependent Density Functional Theory (TD-DFT).

Synthesis of new star-like triply ferrocenylated compounds

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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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Cyclic azomethine imines possessing a beta-aminocarbonyl motif are accessed from simple alkene and hydrazone starting materials. A thermal, concerted alkene aminocarbonylation pathway involving an imino-isocyanate intermediate is proposed and supported by DFT calculations. A notable feature of the process is the steric shielding present in the dipoles formed, which allows for facile purification of the products by chromatography or crystallization. In addition, a fluorenone-derived reagent is reported, which provides reactivity with several alkene classes and allows for mild derivatization of the dipoles into beta-aminoamides, beta-aminoesters, and beta-amino acids.

A tunable route for the synthesis of azomethine imines and beta-aminocarbonyl compounds from alkenes

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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 efficient synthesis of various diborylalkenes such as 1,1-, trans-1,2-, and cyclic 1,2-diborylalkenes from alkenes and diboron was achieved for the first time. Selective preparation of di- and monoborylalkenes was also realized by the appropriate choice of reaction conditions. The reaction was found to proceed via a new mechanism of dehydrogenative borylation through a monoborylpalladium complex bearing an anionic PSiP-pincer ligand as a key intermediate, which realized the efficient borylation without sacrificial hydroboration or hydrogenation of the alkene.

Efficient synthesis of diborylalkenes from alkenes and diboron by a new PSiP-pincer palladium-catalyzed dehydrogenative borylation

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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