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Planar chiral phosphines displaying a new ferrocenophane scaffold have been prepared via a stereoselective approach. The P-cyclohexyl substituted phosphine affords high levels of asymmetric induction in the organocatalytic [3 + 2] annulation reaction between allenes and electron-poor olefins. Copyright

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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-a silicon oxygen radical three carbon ester ferrocene monomer and its preparation method. Double-a silicon oxygen radical three carbon ester ferrocene monomer the chemical structural formula of I shown in the following: the double a silicon oxygen radical three carbon ester ferrocene preparation method of the monomer is 1, 1′ – double-aldehyde ferrocene and 1 – methoxy – 1 – (trimethyl siloxy) – 2 – methyl – 1 – propene in the final ether complex as catalyst under the conditions of the double-a silicon oxygen radical three carbon ester by the reaction of the ferrocene monomer. The invention preparation of double-a silicon oxygen radical three carbon ester ferrocene monomer can be applied to the preparation of an electrically conductive material. (by machine translation)

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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 two new redox active cyclam ligands ferrocenylmethyl-(6-methyl-1,4,8,11tetraazacyclotetradec-6-y1)-amine (L3) and 1,1′-ferrocenylmethyl-bis(6-methyl-1,4,8,11-tetraazacyclotetradec-6-yl)-amine (L4) are reported. The compounds each possess a ferrocenyl group bearing one (L3) or two (L4) appended macrocycles linked by their exocyclic amino groups and the crystal structures of both compounds have been determined. Anion binding of L3 and L4 was investigated by electrochemical titrations where H-bonding to each macrocycle causing a shift in the Fc+/0 redox potential was used as a reporter of guest binding. The ZnII complex of L3 has also been isolated and characterized structurally. These compounds were analysed for their capacity to electrochemically recognize anions in both aqueous and non-aqueous solution, We have found that L3, L4 and [ZnL 3]2+ sense Cl- and AcO- anions in MeCN-CH2Cl2, a function that is lost 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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The capability of metallocene bridges as new organometallic magnetic couplers is evaluated by studying the family of diradicals 2 (M = Fe, Ru) consisting of two purely organic alpha-nitronyl aminoxyl radicals connected by a 1,1?-metallocenylene bridge. Preliminary studies performed with 2-metallocenyl-alpha-nitronyl aminoxyl monoradicals 1 (M = Fe, Ru, Os), as reference compounds, show the presence of a small spin density on the central metal of the metallocenes. This fact makes the metallocene units effective bridges to transmit magnetic interactions by a spin polarization mechanism. The study of the magnetic properties of diradicals 2 in the solid state and in diluted frozen solutions reveals the existence of an intramolecular antiferromagnetic exchange interaction between the radical subunits whose strength is highly dependent on the molecular conformation adopted by the diradical. As shown by crystal data and by ESR measurements, an intramolecular hydrogen bond between the two radical units forces the molecule to adopt a cisoid molecular conformation, which determines that the magnetic interaction occurs by a direct through-space interaction between the two SOMOs of the two radical units along with the classical spin polarization mechanism through the sigma-bonds of the metallocene unit. Lattice constants for both structures are as follows: 1 (M = Fe), C17H21FeN2O2, a = 7.170(1) A, b = 10.135(2) A, alpha = 10.683(2) A, alpha = 88.88(3), beta = 83.42(3), gamma = 79.75(3), triclinic, P1, Z = 2; 2 (M = Fe), C24H32FeN4O4, a = 11.848(3) A, b = 11.785(2) A, c = 17.728(4) A, beta = 106.25(2), monoclinic, P21/n, Z = 4.

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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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Ferrocenyl-chalcones and their bichalcone analogues were characterized by IR and NMR spectroscopy, as well as electrochemically. Their UV?visible spectra were recorded, and the electronic transitions were assigned by time-dependent DFT calculations. The single-crystal X-ray structures were determined for two ferrocenyl bichalcones.

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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 variety of aminomethyl-substituted ferrocenes and the parent compounds (iminomethyl)ferrocenes, azaferrocenophanes, and diferrocenylamines can be selectively synthesized from reductive amination of 1,1?-diformylferrocene or formylferrocene. The optimized one- or two-step reactions have delivered 13 new compounds, isolated in 65-97% yields, which include tertiary (ferrocenylmethyl)amines and azaferrocenophanes by using NaBH(OAc)3 as a mild reducing agent and (iminomethyl)ferrocenes and secondary (ferrocenylmethyl)amines by using LiAlH4. X-ray structures of representative members of these ferrocene derivative families have evidenced the preferred conformation adopted by ferrocene backbones, in which surprisingly the steric hindrance is apparently not systematically minimized. 15N NMR measurements on aminomethyl-substituted ferrocenes and derivatives are provided for the first time, establishing benchmark values ranging from -330 to -305 ppm (nitromethane delta 0 ppm). The cyclic voltammetry of these species evidences two clearly distinct oxidation potentials related to the iron(II) center and the amino function. These aminomethyl-substituted ferrocenes are potentially valuable for further ortho-directed functionalization of ferrocene.

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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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<3.3>(1,1′)Ruthenocenophane-2,14-diene-1,16-dione, <5.5>(1,1′)ruthenocenophane-2,14,17,29-tetraene-1,16-dione and their ferrocenoruthenocenophane homologs were synthesized by using an intramolecular base-catalyzed condensation.

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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 simple chromatography-free method for desymmetrizing ferrocene is described starting from the readily available dialdehyde. Oxidation of 1,1?-ferrocenedicarboxaldehyde in a water/acetonitrile mixture with KMnO4 produced 1?-formyl-ferrocenecarboxylic acid. The same reaction carried out in a water/acetone mixture produced 1?-[(E)-3-oxo- but-1-enyl]-ferrocenecarboxylic acid.

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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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Borane, as a DMS or a THF complex, can efficiently reduce a large range of ferrocenyl derivatives (aldehydes, ketones, ethers, acetals, carboxylic acids, esters,…) if they bear at least one oxygen at a carbon at the alpha position. On the contrary, similar molecules, which contain nitrogen instead of oxygen, do not react with borane.

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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 series of heterobimetallics containing ferrocene and Pd(II) or Pt(II) have been synthesized by oxidative addition of ferrocene-substituted halothiophenes with zerovalent palladium or platinum precursors. The stable solids were thoroughly characterized by elemental analysis, NMR, UV-vis spectroscopy, and cyclic voltammetry. The rich redox chemistry of the complexes depends on the conjugation length that separates the two metal sites. The crystal structure of a platinum sigma-thienyl complex, (C5H5)Fe(C5H4CH=CH-th-Pt(PPh 3)2(Br)) (th = 2,5-disubstituted thiophene) has been determined.

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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