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Nanoparticle-mediated intervalence transfer

Nanoparticle-mediated intervalence transfer was reported with ferrocene moieties that were attached onto the ruthenium nanoparticle surface by ruthenium-carbene pi bonds. The resulting particles exhibited two pairs of voltammetric waves with a potential spacing of about 200 mV and a rather intense absorption peak in the near-infrared range (?1930 nm) at mixed valence. Both features suggested Class II characteristics of the intraparticle intervalence transfer that mainly arose from through-bond interactions between the metal centers. Quantum calculations based on density functional theory showed that the nanoparticle core electrons served as conducting band states for the effective charge delocalization between particle-bound ferrocene moieties.

Nanoparticle-mediated intervalence transfer

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Reference£º
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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Difluoroacetaldehyde N-Triftosylhydrazone (DFHZ-Tfs) as a Bench-Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane

Despite the growing importance of volatile functionalized diazoalkanes in organic synthesis, their safe generation and utilization remain a formidable challenge because of their difficult handling along with storage and security issues. In this study, we developed a bench-stable difluoroacetaldehyde N-triftosylhydrazone (DFHZ-Tfs) as an operationally safe diazo surrogate that can release in situ two low-molecular-weight diazoalkanes, diazoacetaldehyde (CHOCHN2) or difluorodiazoethane (CF2HCHN2), in a controlled fashion under specific conditions. DFHZ-Tfs has been successfully employed in the Fe-catalyzed cyclopropanation and Doyle?Kirmse reactions, thus highlighting the synthetic utility of DFHZ-Tfs in the efficient construction of molecule frameworks containing CHO or CF2H groups. Moreover, the reaction mechanism for the generation of CHOCHN2 from CF2HCHN2 was elucidated by density functional theory (DFT) calculations.

Difluoroacetaldehyde N-Triftosylhydrazone (DFHZ-Tfs) as a Bench-Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane

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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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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. COA of Formula: C12H3Fe. 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

Ferrocenyl oligo(phenylene-vinylene) thiols for the construction of self-assembled monolayers

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.

Ferrocenyl oligo(phenylene-vinylene) thiols for the construction of self-assembled monolayers

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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.Electric Literature of 1271-51-8

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Vinylborane formation in rhodium-catalyzed hydroboration of vinylarenes. Mechanism versus borane structure and relationship to silation

Attempted catalytic hydroboration of (4-methoxyphenyl)ethene 1 with R,R-3-isopropyl-4-methyl-5-phenyl-1,3,2-oxazaborolidine 6 proceeded extremely slowly relative to the 3-methyl analog 2 derived from phi-ephedrine when diphosphinerhodium complexes were employed. With phosphine-free rhodium catalysts, especially the 4-methoxy-phenylethene complex 7, the reaction proceeded rapidly and quantitatively to give only the corresponding (E)-vinylborane 9 and 4-methoxyethylbenzene 8 in equimolar amounts. Isotopic labeling and kinetic studies demonstrated that this reaction pathway is initiated by the formation of a rhodium hydride with subsequent reversible and regiospecific H-transfer to the terminal carbon, giving an intermediate which adds the borane and then eliminates the hydrocarbon product. Further migration of the secondary borane fragment from rhodium to the beta-carbon of the coordinated olefin occurs, followed by Rh-H beta-elimination which produces the vinylborane product and regenerates the initial catalytic species. When the same catalytic reaction is carried out employing catecholborane in place of the oxazaborolidine, an exceedingly rapid turnover occurs. The products are again 4-methoxyethylbenzene and the (E)-vinylborane 23 but accompanied by the primary borane 24 in proportions which vary with the experimental conditions. None of the secondary borane, which is the exclusive product when pure ClRh(PPh3)3 is employed as catalyst, is formed. The product variation as a function of initial reactant concentration was fitted to a model in which the rhodium-borane intermediate in the catalytic cycle undergoes two competing reactions-beta-elimination of Rh-H versus addition of a further molecule of catecholborane. The model demonstrates that a kinetic isotope effect of 3.4 operates in the beta-elimination step, but none is evident in the addition of catecholborane B-D to rhodium. A similar analysis was successfully applied to the catalytic hydrosilylation of 4-methoxystyrene, with HSiEt3, again employing the phosphine-free rhodium catalyst 7; the product distribution between primary silane 29 and vinylsilane 28 was successfully predicted. The results intimate that silation (i.e., the formation of vinylsilanes under the conditions of catalytic hydrosilylation) can best be explained by a Rh-H based mechanistic model rather than the commonly assumed variant on the Chalk-Harrod catalytic cycle. They provide an explanation for the “oxygen effect” on the rate of Rh-catalyzed hydrosilylations.

Vinylborane formation in rhodium-catalyzed hydroboration of vinylarenes. Mechanism versus borane structure and relationship to silation

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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

 

Brief introduction of Vinylferrocene

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Reference of 1271-51-8, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In an article, 1271-51-8, molcular formula is C12H3Fe, belongs to iron-catalyst compound, introducing its new discovery.

Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds

Reactions of Cp2TiMe2, with the ester derivatives of organometallic sandwich compounds (n5-RC5H4)Fe(n5-C5H5) and (n5-RC5H4)Co(n4-C4Ph4) (R=ester groups) gave products having R=C(CH2)Me, instead of the expected vinyl ethers indicating conversion of the ester units by Cp2TiMe2 to methyl ketones followed by methylenation. A reaction of Cp2TiMe2 with the diester (n5-RC5H4)Co(n4-C4Ph3R)(R=C(O)OMe) also gave similar results. The study has also been successfully extended to metal sandwich derived amides, thio and seleno esters. By controlling the amount of Cp2TiMe2, the reactions were also stopped at the methyl ketone stage and the methyl ketones were isolated in good yields and characterized. The method provides an easy and direct access to convert organometallic sandwich derived esters and related compounds to 1-methylvinyl derived products.

Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds

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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

 

Brief introduction of Vinylferrocene

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Measurement of double-layer forces at the polymer film/electrolyte interfaces using atomic force microscopy: Concentration and potential-dependent interactions

The forces between colloidal probes and several polymer films were measured by atomic force microscopy in the presence of a series of electrolyte solutions. For Nafion films using a negatively charged silica tip, a repulsive force was obtained at different concentrations of NaClO4. A similar result was obtained for an anion exchange membrane with a positively charged probe. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was employed to calculate the surface potential and hence, the surface charge. The surface charge density (a??0.3I?C/cm2) was independent of electrolyte concentration. The slope for plot of potential drop vs In[cs] was a??0.020 V. A theoretical treatment based on GCS theory was employed to account for the above results. For a poly(vinylferrocene) (PVF) film, potential-dependent force curves were obtained, which were qualitatively different from that previously reported for an electronically conducting polymer film electrode.

Measurement of double-layer forces at the polymer film/electrolyte interfaces using atomic force microscopy: Concentration and potential-dependent interactions

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Design, synthesis and characterization of ferrocene based V-shaped chromophores with modified nonlinear effect

In order to prepare D-pi-A-pi-D analogs have the ability to use in optical applications, 4H-pyran fragment conjugated with two styryl groups and their combination play pi-spacer role between donor and acceptor groups. Malononitrile and 1, 3-indandione play as acceptor groups and ferrocene nuclei was chosen as donor group. 1H and 13C NMR, FT-IR and mass spectroscopy and CHN analysis were used to confirm the structure of synthesized compounds. Electrochemical, photochemical and photophysical properties of these compounds were studied. The third order nonlinear refractive index, n2, and nonlinear absorption coefficient, beta, of synthesized chromophores were assessed by the open and closed aperture Z-scan measurements, respectively. The quantum chemistry study was performed on synthesized compounds with the DFT approach. The theoretical and experimental results show that these compounds can be considered as candidates to be used in optical applications.

Design, synthesis and characterization of ferrocene based V-shaped chromophores with modified nonlinear effect

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Noncovalent linkage of telechelic oligo(dimethylsiloxanes) via end group attachment of host-cyclodextrins and guest-adamantanes or guest-ferrocenes

In this article, we report the noncovalent linkage of terminal substituted oligo(dimethylsiloxanes) bearing cyclodextrins (CD) as host endgroups and adamantan or ferrocene, respectively, as guest endgroups. Structural characterization was performed by 1H NMR-, IR-, and mass spectroscopy. Electron microscopy studies show significant differences in the surface structure of the individual derivatives. In addition, the ferrocene-terminated di-and poly(dimethylsiloxanes) are distinguished by a red-ox activity and reversibility, which also makes the complexes between the ferrocene- and CD functionalized siloxanes switchable via electrochemical stimuli. The evidence for a successful complexation of the end groups, and thus the successful supramolecular formation of the siloxane strands, was even performed by shift of the protons in the 1H NMR spectra.

Noncovalent linkage of telechelic oligo(dimethylsiloxanes) via end group attachment of host-cyclodextrins and guest-adamantanes or guest-ferrocenes

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Reference£º
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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“Polysiloxane-Pd” nanocomposites as recyclable chemoselective hydrogenation catalysts

Polysiloxane-encapsulated “Pd”-nanoclusters were generated by reduction of Pd(OAc)2 with polymethylhydrosiloxane, which functions as a reducing agent as well as a capping material for production and stabilization of catalytically active “Pd”-nanoparticles. Chemoselective hydrogenation of functional conjugated alkenes was achieved by in-situ- or ex-situ-generated polysiloxane-stabilized “Pd”- nanoclusters under mild reaction conditions in high yields. Electron microscopy, UV-vis, and NMR studies of the reaction mixture during the catalytic transformation were performed and, in conjunction with catalyst poisoning experiments, demonstrated unequivocally the role of polysiloxane-encapsulated “Pd”-nanoclusters as the real catalytic species. The recyclability of the “Pd”-nanoclusters was established by reusing the solid left after the reaction.

“Polysiloxane-Pd” nanocomposites as recyclable chemoselective hydrogenation catalysts

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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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Synthesis of alpha-arylalkylferrocenes through cesium fluoride-promoted coupling of arylboronic acids with N-tosylhydrazones

A cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted alpha-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C?B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the alpha-arylalkylferrocenes compounds were also obtained on a multi-gram scale.

Synthesis of alpha-arylalkylferrocenes through cesium fluoride-promoted coupling of arylboronic acids with N-tosylhydrazones

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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