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Ferrocene-bridged bisporphyrins have been synthesized by the condensation of corresponding dipyrromethane-derived diols with a bisdipyrromethane. Purification of the final compounds has been achieved without chromatography. The specific geometry of these bisporphyrins makes them valuable starting points for building complex molecular and supramolecular structures. In particular it provides a core to which multiple sites of attractive intermolecular interactions can be attached thereby creating compounds predisposed to form complex networks by association. We have studied the structure of bis-1,1?-(porphyrinyl)ferrocenes by 1H NMR, UV-Vis and electrochemistry. Results have shown that complex dynamic processes occur in these molecules (which may involve conformers, formation of H-aggregates and tautomers) and that they have non-typical electrochemical behaviour. The Royal Society of Chemistry 2005.

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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.

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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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2-(Ferrocenylmethyl)amino-2-methylpropan-1-ol was synthesized and converted to the respective ammonium bromide ([1H]Br ? 2) and dihydrogenphosphate ([1H]H2PO4 ? 3). The solid-state structures of 1, 2 and the solvated salt 3 · 1/6Et2O (3a) have been determined by X-ray diffraction. The solid-state assemblies of 1 and 2 are dominated by infinite ladder-like arrays interconnected by hydrogen bonds whereas the solid-state structure of 3a is built up from linear hydrogen-bonded dihydrogenphosphate chains, which are interlinked via hydrogen bonds to the cations [1H]+ into a complicated three-dimensional network. Compound 1 and its interactions with Bu4NBr and Bu4NH2PO4 in solution were further studied by electrochemical methods and NMR titrations.

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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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A reaction between cynichrodenoic acid, (eta5-C5H4COOH)Cr(CO)2NO (6) and phosphorus pentachloride produces cynichrodenoyl chloride (11) in high yield.Subsequent reaction of 11 with sodium azide affords cynichrodenoyl azide (12), which undergoes Curtius rearrangement to form cynichrodenyl isocyanate (13).Subsequent hydrolysis of isocyanate 13 in aqueous KOH solution yields aminocynichrodene (14).Azide 12 also undergoes Curtius rearrangement in the presence of benzyl alcohol to produce benzyl N-cynichrodenylcarbamate (15).Reactions of acid chloride 11 with ammonia, dimethylamine or aniline lead to the corresponding carboxamides (16-18).Amide 16 is readily dehydrated to produce cynichrodenecarbonitrile (19).Reactions of acid chloride 11 with either benzyl alcohol or hydroxymethylferrocene generate the corresponding esters (20-21), whereas treatment of a tetrahydrofuran solution of 11 with pyridine affords cynichrodenecarboxylic anhydride (22) in low yield.Reactions of acetylcynichrodene (2) with organolithium reagents, leading to both carbonyl addtion and condensation products, have been investigated.Treatment of 2 with lithium diisopropylamide in diethyl ether solution produces the self-condensation product 1,3-dicynichrodenyl-but-2-en-1-one (24).Acetyl derivative 2 and benzaldehyde also undergo Claisen-Schmidt condensation in the presence of lithium diisopropylamide to afford cinnamoylcynichrodene (27).

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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 series of liquid-crystalline ferrocene derivatives, Fe2 (X = H, OH; n = 3 to 12), were obtained by the condensation of 1,1′-bishydrazondiacetylferrocene with p-alkoxybenzoyloxybenzaldehydes.According to DSC and polythermic microscopy, all of the compounds exhibit an enantiotropic nematic mesophase in the 150-230 deg C temperature range.A polycrystalline transition precedes the nematic transition.The liquid crystalline properties of the obtained compounds were investigated with respect to the number of carbon atoms in the terminal alkyl chain and the terminal hydroxy group.The composition and structure of the obtained compounds were determined by elemental analysis and IR and NMR spectroscopy. – Key words: liquid crystals; ferrocene; metallomesogenes.

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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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The title compounds were synthesized in quantitative yields by interacting alpha-hydroxyalkyl ferrocenes with polyfluoroalkyl benzimidazoles in an aqueous-organic medium in the presence of HBF4. The resulting diastereomers and enantiomers were resolved using HPLC on silica bonded chiral stationary phases based on chiral cyclodextrins and cyclic antibiotics. The X-ray determination of molecular and crystal structure of 1-ferrocenylmethyl-2-(trifluoromethoxyfluoromethyl)benzimidazole (1) was carried out.

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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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Hydrosilylation of vinyl ferrocene with allylhydridopolycarbosilane was used to synthesize a processable hyperbranched polyferrocenylcarbosilane (HBPFCS), which was characterized by combination of gel permeation chromatography, Fourier transform infrared (FT-IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. The polymer-to-ceramic transformation of the HBPFCSs was then investigated by FT-IR and 13C MAS NMR spectroscopy as well as by thermal gravimetric analysis (TGA). A self-catalytic effect of ferrocenyl units in the HBPFCS skeleton on dehydrocoupling was found during a curing process at 170C resulting in a high ceramic yield of ca. 80% at 1200C in Ar. Finally, microstructures and magnetic properties of the final ceramics were studied by techniques such as X-ray diffraction, energy dispersive spectroscopy, Raman spectroscopy, transmission electron microscopy and vibrating sample magnetometry. The final ceramic (pyrolysis temperature ?900 C) is characterized by a microstructure comprised of a SiC/C/Fe nanocomposite. Turbostratic carbon layers located at the segregated alpha-Fe crystal boundary avoid interdiffusion and explain the exclusive existence of alpha-Fe in a SiC/C matrix even at 1300 C. Variations of the iron content in the HBPFCSs and of the pyrolysis conditions facilitate the control of the composition and ceramic micro/nanostructure, influencing in particular magnetic properties of the final SiC/C/Fe nanocomposite ceramic.

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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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Dehydrobromination of cis and trans isomers of 1-bromo-2-ferrocenylcyclopropanes affords 1-ferrocenylcyclopropene. Its protonation with HBF4 results in 1-ferrocenylcyclopropylium tetrafluoroborate, which alkylates N,N-dimethylaniline in para position to yield 1-(p-dimethylaminophenyl)-1-ferrocenylcyclopropane. 1-Ferrocenylcyclopropene reacts with 1,3-diphenylisobenzofuran to give the classical [4+2]-cycloaddition product. Its structure as exo-2-ferrocenyl-1,5-diphenyl-6,7-benzo-8-oxatricyclo [3.2.1.02.4]oct-6-ene was established based on the data from X-ray diffraction analysis.

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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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We show here that the disubstituted ferrocenyl chalcones 1 and 2 are good electrochemical sensors for calcium and barium in CH3CN. However, these two triflate salts are detected in a different way by both ligands. To clarify this point, a thorough and informative NMR study of the ligand-salt interactions is presented. The unusual shapes of the titration curves obtained depend on both the ligand and cation used. For example, they illustrate that ligand 1 mainly interacts with the metal by its CO functions, while ligand 2 also interacts by its azacrown groups. These curves also reflect complex equilibriums in solution involving several ligand-salt adducts detected by mass spectrometry. To evaluate the strength of these interactions, the association constants of all the species formed have been determined by fitting the NMR data. It is noteworthy that changing the diethylamino groups in molecule 1 by the azacrown residue enhances the selectivity for the calcium salt, as pointed out by the value of the association constant of the 2Ca2+ species. The synthesis of the protonated counterparts 3 and 4 was useful to clarify the electrochemical behaviour of 1 and 2. Although the two ligand-salt interactions present several common points, the whole results obtained allow us to propose an original explanation for the difference observed between the Ca2+ and Ba2+ electrochemical sensing.

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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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Nitrogen doped multi-walled carbon nanotubes (N-CNTs) were synthesized by the solid state pyrolysis of ferrocenylmethylimidazole or a mixture of ferrocene (FcH)/i-methylimidazole (i = 1, 2 and 4) at 800 C at different ratios in sealed quartz tubes. Transmission electron microscopy (TEM) images confirmed that the carbon nanotubes (CNTs) obtained were doped with nitrogen to give nitrogen doped multi-walled CNTs (N-CNTs). N-CNTs showed bamboo-like structures for the CNTs produced from both ferrocenylmethylimidazole and the mixtures of FcH/i-methylimidazole at varying ratios. The study revealed that the different imidazoles produced different types/size distributions of shaped carbon nanomaterials (SCNMs) including N-CNTs with different diameters. An investigation of the bamboo structures revealed that the three methylimidazole isomers led to tubes with different individual bamboo compartment distances and different morphologies including different N contents. This confirms that the synthesis of N-CNTs is determined by fragments (ratios, types) produced by decomposition of reactants at high temperature.

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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