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The rigid [6]ferrocenophane, L1, was synthesised by condensation of 1,1?-ferrocene dicarbaldehyde with trans-1,2-diaminocyclohexane in high dilution at r.t. followed by reduction. When other experimental conditions were employed, the [6,6,6]ferrocenephane (L2) was also obtained. Both compounds were characterised by single crystal X-ray crystallography. The protonation of L1 and its metal complexation were evaluated by the effect on the electron-transfer process of the ferrocene (fc) unit of L1 using cyclic voltammetry (CV) and square wave voltammetry (SWV) in anhydrous CH3CN solution and in 0.1 M nBu4NPF6 as the supporting electrolyte. The electrochemical process of L1 between -300 and 900 mV is complicated by amine oxidation. On the other hand, an anodic shift from the fc/fc+ wave of L1 of 249, 225, 81 and 61 mV was observed by formation of Zn2+, Ni2+, Pd2+ and Cu2+ complexes, respectively. Whereas Mg2+ and Ca2+ only have with L1 weak interactions and they promote the acid-base equilibrium of L1. This reveals that L1 is an interesting molecular redox sensor for detection of Zn2+ and Ni2+, although the kinetics of the Zn2+ complex formation is much faster than that of the Ni2+ one. The X-ray crystal structure of [PdL1Cl2] was determined and showed a square-planar environment with Pd(II) and Fe(II) centres separated by 3.781(1) A. The experimental anodic shifts were elucidated by DFT calculations on the [ML1Cl2] series and they are related to the nature of the HOMO of these complexes and a four-electron, two-orbital interaction.

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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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Condensation of aromatic, isoxazole, and ferrocene aldehydes as well as 1,1?-diacetylferrocene with 5-(4-methylphenyl)isoxazole-3-carbohydrazonamide afforded various N-substituted azines with molecular fragments of the corresponding aldehydes or diacetylferrocene.

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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 carbon nanotubes (N-CNTs) have been synthesized at 850 C via a CVD deposition technique by use of three ferrocenyl derivative catalysts, i.e. para-CN, -CF3 and -Cl substituted-phenyl rings. The synthesized catalysts have been characterized by NMR, IR, HR-MS and XRD. The XRD analysis of the para-CF3 catalyst indicates that steric factors influence the X-ray structure of 1,1?-ferrocenylphenyldiacrylonitriles. Acetonitrile or pyridine was used as carbon and nitrogen sources to yield mixtures of N-CNTs and carbon spheres (CS). The N-CNTs obtained from the para-CF3 catalysts, in pyridine, have the highest nitrogen-doping level, show a helical morphology and are less thermally stable compared with those synthesized by use of the para-CN and -Cl as catalyst. This suggests that fluorine heteroatoms enhance nitrogen-doping in N-CNTs and formation of helical-N-CNTs (H-N-CNTs). The para-CF3 and para-Cl catalysts in acetonitrile yielded iron-filled N-CNTs, indicating that halogens promote encapsulation of iron into the cavity of N-CNT. The use of acetonitrile, as carbon and nitrogen source, with the para-CN and -Cl as catalysts also yielded a mixture of N-CNTs and carbon nanofibres (CNFs), with less abundance of CNFs in the products obtained using para-Cl catalysts. However, para-CF3 catalyst in acetonitrile gave N-CNTs as the only shaped carbon nanomaterials.

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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 number of ether- and thioether-substituted ferrocenes (1,1?-bis(1,3-dioxane-2-yl)ferrocene 1, 1,1?-bis(5-methyl-1,3- dioxane-2-yl)ferrocene 2, 1,1?-bis(4-methyl-1,3-dioxane-2-yl)ferrocene 3, 1,1?-bis[(R)-(-)-4-methyl-1,3-dioxane-2-yl]ferrocene 4, 1,1?-bis(4,6-dimethyl-1,3-dioxane-2-yl)ferrocene 5, and 1,1?-bis(1,3-dithiane-2-yl)ferrocene 6) were synthesised by direct condensation of 1,1?-diformylferrocene with the corresponding diols or dithiols. The crystal structures of 1, 5a, 5b, and 6 were determined by X-ray diffraction studies. Electrospray ionisation mass spectrometry was used to investigate the binding behaviour of 1 and 6 toward alkali as well as transition metal cations. The dioxane-containing species 1 showed high affinity toward Li+ and Na+, whereas the dithiane derivative 6 bound, as expected, preferentially to Hg2+. The Royal Society of Chemistry 2003.

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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 new family of Ruthenium(II)-arene complexes of lidocaine of formula [RuII(eta6-p-cymene)Cl(LC)](PF6), 1, [RuII(eta6-p-cymene) (C[tbnd]CFc) (LC)](PF6), 2, [RuII(eta6-p-cymene) (C[tbnd]CFcIP) (LC)](PF6), 3 (LC: lidocaine, FcC[tbnd]CH: ferrocenyl acetylene, C[tbnd]CFcIP: 1?-(phenanthro[9,10-d]imidazole) ferrocenyl-1-acetylene) were prepared and characterized by ESI-MS spectrometry, elemental analysis, IR,1H and13C NMR spectroscopy. The photocytotoxicity of 1?3 was studied with visible light (400?700 nm) against a panel of human cancer cell lines namely, A-375 (human melanoma), HeLa (human cervical cancer) and MCF-7 (human breast cancer) cancer cells. The photoactivity follows the order 1 < 2 < 3 with 2 and 3 having IC50values in A-375 (melanoma) cells in the low micromolar range. These complexes interact with calf thymus DNA. The photocleaving pUC19 DNA of complexes with visible light (400?700 nm) was studied and the results exhibited the active involvement of superoxide and hydroxyl radicals as the reactive oxygen species (ROS) in the DNA photocleavage reactions. These complexes interact with calf thymus DNA via intercalative mode that binding constants vary in the order: 3 > 2 > 1. The complexes 2 and 3 were photoactivated in A-375 cells by visible radiation and analyzed by alkaline single-cell gel electrophoresis.

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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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Alkenylferrocenes, FcCHCHCHCH2 have been synthesized from formylferrocene and allyl halides using beta-SnO and Pd(0) or Pt(II) as co-catalyst in organic aqueous medium. Monoallylated products have been isolated by similar reaction with 1,1?-bis-formylferrocene. These serve as potential precursors for multinuclear ferrocenophanes with extended conjugated ene-spacer.

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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 invention relates to a double-allyl three-carbon ester ferrocene monomer and its preparation method. In order to 1, 1 ‘- double-(1 – methoxy – 3 – butenyl) ferrocene and 1 – methoxy – 1 – (trimethyl siloxy) – 2 – methyl – 1 – propylene as the raw material, at the low temperature, boron trifluoride ether complex adds by drops three, to obtain 1, 1’ – double-[1 – (1 – methoxy carbo- acid radical – 1 – methyl – ethyl) – 3 – ene butyl] ferrocene compound; diene propyl substituted three-carbon methyl ester ferrocene not only can be used for the melt polycondensation of the polyester, but also has the double bond giving it take part in the polymerization reaction capability of the, therefore is a novel ferrocene base monomer. (by machine translation)

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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 bitopic ligand 1,1?-bis(dipyrazol-1-ylmethyl)ferrocene, Fe[C 5H4CH(pz)2]2 (1; pz = pyrazolyl ring), has been prepared by the reaction of 1,1?-ferrocenedicarbaldehyde and 1,1?-carbonyldipyrazole. In the solid state, the bis(pyrazolyl) methane moieties are in an antiperiplanar eclipsed orientation. The molecules are organized into a three-dimensional array by pi…pi, weak C-H-…N hydrogen bonding, and C-H…pi interactions. The reactions between 1 and AgBF4, AgPF6, AgSO3CF 3, or AgSbF6 yield {Fe[C5H 4CH(pz)2]2AgBF4}n (2), {Fe[C5H4CH(pz)2]2AgPF 6}n (3), {Fe[C5H4CH(Pz) 2]2AgSO3CF3}n (4), and {Fe[C5H4CH(pz2]2AgSbF 6}n (5), respectively. The solid-state structures consist of coordination polymers with compounds 2 and 3 arranged in helical chains, while the chains in 3·1/2Et2O, 4·1.5C6H 6,5·1/2Et2Et2O, and 5·1/2C 6H6 are nonhelical. In these structures, the ferrocenyl groups adopt a similar orientation, where the angle between CH(pz)2 groups is confined to the range of 85-99 and the silver pyrazolyl coordination spheres are also in very similar distorted-tetrahedral arrangements. Both structural types form three-dimensional supramolecular structures organized by weak hydrogen bonds, pi…pi stacking, and CH…pi interactions. In the helical form, the anions reside in the pockets formed by the close-packed chains, whereas in the nonhelical form, sizable channels, which contain the solvent molecules and the anions, are located between the chains.

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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 facile synthesis of new conjugated oligo-ferrocenyl compounds is described. The synthetic method consists of a two step procedure, which combines olefination by the Wittig procedure and Pd-mediated C-C coupling, leading to high yields of tri- and penta-ferrocenyl complexes. The crystal structures of the 1,1?-bissubstituted ferrocenyl precursors are described. The electrochemical analysis of the compounds obtained, reveals that the peripheral ferrocenyl units display an equivalent redox behavior, with a large separation of the peak corresponding to the central ferrocenyl unit.

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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 syntheses and characterization of heterodi- and heterotrimetallic complexes of general formulas [Pd{[(eta5-C5H 3)-C(R)=N-R?]Fe[(eta5-C5H 4)-C(R)=N-R?]}Cl(PPh3)] [Pd{[(eta5-C5H3)C(C6H 5)=N-C6H5]Fe[(eta5-C 5H4)-C(O)=N-C6H5]}Cl(PPh 3)], and [Pd2{Fe[(eta5-C5H3)-C(R)= N-R?]2}Cl2(PPh3)2] {with R = H, CH3, or C6H5 and R?= phenyl or benzyl groups} are reported. The X-ray crystal structure of the meso-form of [Pd2{Fe[(eta5-C5H3)-C(CH 3)=N-C6H5]2}Cl2(PPh 3)2] (2b) is also described.

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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