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We report the large scale syntheses and ‘oxidative purification’ of fcI2, fcBr2 and FcBr (fc = ferrocene-1,1?-diyl, Fc = ferrocenyl). These valuable starting materials are typically laborious to separate via conventional techniques, but can be readily isolated by taking advantage of their increased E1/2 relative to FcH/FcX contaminants. Our work extends this methodology towards a generic tool for the separation of redox active mixtures.

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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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2,4,6-Tris(1-diphenylphosphanyl-1?-ferrocenylene)-1,3,5-triazine (1) coordinates all three coinage metal(I) ions in a 1:1 tridentate coordination mode. The C3-symmetric coordination in both solid state and solution is stabilised by an uncommon cation?pi interaction between the triazine core and the metal cation. Intramolecular dynamic behaviour was observed by variable-temperature NMR spectroscopy. The borane adduct of 1, 1BH3, displays four accessible oxidation states, suggesting complexes of 1 to be intriguing candidates for redox-switchable catalysis. Complexes 1Cu, 1Ag, and 1Au display a more complicated electrochemical behaviour, and the electrochemical mechanism was studied by temperature-resolved UV/Vis spectroelectrochemistry and chemical oxidation.

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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 and metal coordination chemistry of a phosphine- and thiolate-substituted ferrocenediyl ligand were discussed. Bridged dimeric species, with the thiolate S adopting a binucleating role were found to be observed for Pd(II) and Rh(I) metal centers while a mononuclear, square planar Ni(II) complex was formed on reaction of the ligand with [Ni-(TMEDA)Me2]. It was found that the rhodium complexes with phosphorus-sulfur donor ligands showed excellent activities and stability as methanol carbonylation catalysts.

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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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Highly effective asymmetric hydrogenation of various ferrocenyl ketones, including aliphatic ferrocenyl ketones as well as the more challenging aryl ferrocenyl ketones, was realized in the presence of a Ru/diphosphine/diamine bifunctional catalytic system. Excellent enantioselectivities (up to 99.8% ee) and activities (S/C = 5000) could be obtained. These asymmetric hydrogenations provided a convenient and efficient synthetic method for chiral ferrocenyl alcohols, which are key intermediates for a variety of chiral ferrocenyl ligands and resolving reagents.

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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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Isomeric diborylated ferrocenes featuring 1,1?-, 1,2-, and 1,3-substitution patterns have been targeted via a combination of electrophilic aromatic substitution and directed ortho-lithiation protocols. While none of these systems are competent for the Lewis acid chelation of fluoride, related systems featuring a mixed B/Si acceptor set capture 1 equiv of fluoride via a Si-F-B bridging motif.

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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 novel, unsymmetrical 1,1?-disubstituted ferrocenediyl ligand, 1-(diphenylphosphino)-1?-(methoxy)ferrocene (3), featuring phosphine and ether substituents has been synthesized via two different routes and structurally characterized. Its coordination chemistry was investigated by reaction with Rh(I), Cu(I), and group 10 metal precursors. With Ni(II) precursors, chelating complexes are formed in high yield, whereas with Pd(II) and Pt(II) precursors, either chelating complexes or monodentate bis ligand complexes with trans phosphorus ligation may be formed depending on the reaction conditions and metal precursor employed. A similar monodentate trans phosphorus-ligated complex is observed with Rh(I), whereas with Cu(I) precursors, a phosphorus-ligated monodentate bis ligand complex with a coordinated acetonitrile was obtained. Preliminary studies show that 3, in combination with either Pd(II) or Pd(0) precursors, can act as a catalyst for the Suzuki coupling reaction.

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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 development of a practical synthesis of 1?-(diphenylphosphino)-1-aminoferrocene (2) and its P-borane adduct (2B) allowed the facile preparation of 1?-(diphenylphosphino)-1-isocyanoferrocene (1). This compound combining two specific soft-donor moieties was studied as a ligand for univalent Group 11 metal ions. The reactions of 1 with AgCl at 1:1 and 2:1 molar ratios only led to the coordination polymer [Ag2(mu-Cl)2(mu(P,C)-1)]n (6), while those with Ag[SbF6] provided the dimer [Ag2(Me2CO-kappaO)2(mu(P,C)-1)2][SbF6]2 and the quadruply-bridged disilver complex [Ag2(mu(P,C)-1)4][SbF6]2 (8), respectively. Addition of 1 to [AuCl(tht)] (tht = tetrahydrothiophene) afforded the mono- and the digold complex, [AuCl(1-kappaP)] (9) and [(mu(P,C)-1)(AuCl)2] (10), depending on the reaction stoichiometry. Finally, the reaction of 1 with [Au(tht)2][SbF6] or halogenide removal from 9 with AgNTf2 led to cationic dimers [Au2(mu(P,C)-1)2]X2 (11, X = SbF6 (a) or NTf2 (b)). Catalytic tests in the Au-mediated isomerization of (Z)-3-methylpent-2-en-4-yn-1-ol to 2,3-dimethylfuran revealed that 11a and 11b are substantially less catalytically active than their analogues containing 1?-(diphenylphosphino)-1-cyanoferrocene as the ligand, most likely due to a stronger coordination of the isonitrile moiety, which prevents dissociation of the dimeric complexes into catalytically active monomeric species.

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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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Key bromoferrocenes have been prepared using a simple, yet effective, lithiation and quench methodology. These include 1,2,3-tribromoferrocene and 1,2,3,4,5-pentabromoferrocene. The synthetic method reported can be applied to make a broad range of bromoferrocenes.

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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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We report the synthesis of mono- and 1,1?-difluoro-substituted metallocenes (ferrocene, ruthenocene) and of asymmetrical 1,1?-disubstituted ferrocenes with one substituent being fluorine. Lithiation of metallocenes and subsequent addition of the fluorinating agent NFSI gave the fluorinated metallocenes after optimization of the experimental conditions. All new compounds were comprehensively characterized and the cyclic voltammograms of fluoro- and 1,1?-difluoroferrocene were recorded and compared to other mono- and dihalogenated ferrocenes. Half-wave potentials of +106 mV and +220 mV vs. FcH0/+ were obtained for monofluorinated species and difluorinated ferrocene, respectively. Both values are remarkably low compared to the other halogenated ferrocenes (Cl, Br, and I). Finally, 1-bromo-1′-fluoro-ferrocene turns out to be an ideal starting material for further fluoro-substituted ferrocene 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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Spectroscopic and photochemical studies of several benzoyl-functionalized ferrocene complexes in nonaqueous solvents are reported. Bands observed above 300 nm in the electronic absorption spectrum of the unsubstituted complex, Fe(n5-C5H5)2, and assigned to ligand field transitions shift to longer wavelengths and intensify upon introduction of a benzoyl group into one or both cyclopentadienide rings. Such .behavior suggests that these transitions have acquired some charge-transfer character. Visible-light (546 nm) irradiation of l.l’-dibenzoyl-ferrocene, III, dissolved in CH3CN, CH3OH, or ethyl alpha-cyanopropionate causes ring-metal cleavage to produce the benzoylcyclopentadienide ion, C6H5C(O)C5H4-, and the corresponding half-sandwich cationic complex, Fe[(n5-C5H4)C(O)C6H 5](S)3+ (S is solvent). The disappearance quantum yield, odis, for III is 0.45 in CH3OH and 0.28 in ethyl alpha-cyanopropionate and is unaffected by the presence of dissolved O2, added H2O (10 000 ppm), or added methanesulfonic acid (30 ppm). l,l?-Dibenzoylferrocenes containing substitutents on both phenyl rings undergo photoinduced ring-metal cleavage in CH3OH with odis values very similar to that of III, while monobenzoyl-ferrocenes are appreciably less photoreactive. A mechanism that accommodates the photochemical behavior of benzoyl-functionalized ferrocene complexes is discussed. In addition, a previous suggestion concerning the role of III in the photoinitiated anionic polymerization of an alpha-cyanoacrylate monomer is reconsidered in light of the present study.

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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