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A series of novel 2-ferrocenyl-3,4-dihydropyrans were synthesized in good to excellent yields through three-component reaction of vinylferrocene, 1,3-dicarbonyl compound and formaldehyde near room temperature under catalyst-free conditions. The obtained ferrocenyl dihydropyrans can also react readily with indole in the presence of alum, providing a ring-opening product in high yield, and this result opens an effective way to access a new class of complex ferrocenyl derivatives.

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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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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.

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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 trifluoromethylcarbene (:CHCF3) was found to be conveniently generated from (2,2,2-trifluoroethyl)diphenyl-sulfonium triflate (Ph2S+CH2CF3 -OTf), which was successfully applied in Fe-catalyzed cyclopropanation of olefins, giving the corresponding trifluoromethylated cyclopropanes in high yields.

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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 synthesis of a C2 symmetric 1,1? ,2,2?-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1?-bis(hydroxymethyl)ferrocenes and 1,1?-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.

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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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Compounds 1,2-bis[(eta5-cyclopentadienyl)dicarbonylnitrosylchromium]ethene (7) (hereafter called 1,2-dicynichrodenylethene) and 1,2-diferrocenylethene (10) were prepared from formylcynichrodene (3) and formylferrocene (9), respectively, via the McMurry’s low-valent titanium coupling method. Compounds (eta5-vinylcyclopentadienyl)dicarbonylnitrosylchromium (6) and vinylferrocene (11) were obtained by the dehydration of the corresponding alcohols. The structure of 7 was solved by an X-ray diffraction study: space group, P21/c; monoclinic; a=6.379(5), b=11.295(3) and c=11.9352(24); Z=2. It turns out that compound 7 adopts a transoid conformation at the ethenylene bridge and the two cyclopentadienyl rings are coplanar. The nitrosyl group in each cynichrodenyl moiety of 7 is located at the side towards the corresponding ethenylene carbon atom with a twist angle of 46.5. The chemical shifts of H(2)-H(5) protons and C(2)-C(5) carbon atoms of a series of vinyl derivatives of compounds bearing cyclopentadienyl rings have been assigned using two-dimensional HetCOR-NMR spectroscopy. For the derivatives of cynichrodene (1) and ferrocene, it was found that the shielding of C(2,5) and C(3,4) carbon atoms is parallel to the shielding of the ortho- and para-carbon atoms of benzene derivatives. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of 13C-NMR data. Surprisingly, the vinyl group donates electron density to the adjacent cynichrodene moieties rather than withdraws from them.

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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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It has been discovered that ferrocenyl substituted heterocyclic compounds have wide scope of restorative methodology. The combination of ferrocenyl substituted pyrazole is the new class in these compounds with upgraded natural activity. This work center around blend of ferrocenyl substituted pyrazoles through novel course. The combination of 1-phenyl-3-ferrocenyl-pyrazole was examined including addition-cyclocondensation like response conditions. The response continued through three phases using of expansion cyclo-buildup of acetyl ferrocene with phenyl hydrazine pursued by cyclizing reagent iodine with NaHCO3. In both syntheses, each time single product isolated having good yields (87 and 79 %). Ferrocenyl substituted pyrazoles were examined by spectroscopic techniques (1H NMR, IR, MS) and their biological properties have been screened.

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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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Ion exchange of ferro/ferricyanide into oxidized polyvinylferrocene (PV-Fc) films occurs upon repetitious cycling of a PV-Fc film between its oxidized and reduced forms in the presence of either Fe(CN)63- and Fe(CN)64-. The ion exchange is evident from cyclic voltammetry and the response of a quartz crystal microbalance coated with a PV-Fc film. Insertion of the multiply charged anions appears to result in deactivation of polyvinylferrocene sites, with the exchanged films initially exhibiting voltammetric waves due to confined ferro(ferri)cyanide. Prolonged cycling of the exchanged films causes complete passivation of the films towards redox species in the film, as well as solution species, suggesting extensive electrostatic cross-linking by the multiply charged anions. Coulometric experiments suggest that approximately one ferro(ferri)cyanide exchanges for three PV-Fc redox sites. The visible spectra of the exchanged films after prolonged cycling suggests the presence of prussian blue-like species in the polymer film which presumably arise from decomposition of the polymer.

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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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tetraphenylcyclobutadienecobalt(I) reacts with lithium tetrachloropalladate(II) in the presence of sodium acetate to give an ortho-palladated binuclear complex.The ?-bonded structure of the complex was confirmed by studies of the IR and 1H-NMR spectra and of the reactions with triphenylphosphine, thalium(I) acetylacetonate, and lithium aluminum deuteride.The reactions of the ?-bonded complex with carbon monoxide and olefins have been examined.

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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.

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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 this paper, authors focus the synthesis of conjugated unsymmetrical stilbenoid dendrimers by Heck and Horner-Wadsworth-Emmons coupling. In UV?visible absorption spectrum, the intensity of the absorption increases with increase in the generation of dendrimers. Further, bathochromic shift is observed on increasing the generation of the dendrimer from zero to first due to the greater widening of the energy gap between pi-pi* orbitals of the dendrimer system. Interfacial charge transport kinetics such as resistance, chemical capacitance and relaxation lifetime of the fabricated dye-sensitized solar cells (DSSC) are investigated using Nyquist and Bode phase plots by electrochemical impedance spectroscopy. Reduced electron relaxation lifetime (taue) of 1.83 ms (LiI + 7) and 1.04 ms (LiI + 8) provides efficient charge injection and thus reducing recombination process in the device. The performance of DSSC fabricated using unsymmetrical conjugated dendrimers with iodide electrolyte shows higher power conversion efficiency (PCE) than standard LiI based device. Two fold increments are achieved in PCE with first generation unsymmetrical dendrimers compared to their zeroth counterpart. The first generation unsymmetrical dendrimer 8 shows better PCE of 9.037% than all other synthesized dendrimers in the newly fabricated DSSC.

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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