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Acylferrocenes 2a-c reacted with ortho-aminoarylaldehydes 1a-e via the Friedlnder condensation reaction to afford the corresponding ferrocenylquinolines 3a-o in moderate yields in the presence of sodium ethoxide (30mmol%) under mild reaction conditions. Under the same reaction conditions, 1,1-diacetylferrocene 2d and 1,1-dipropionylferrocene 2e reacted with ortho-aminoaldehydes 1a-e to afford the corresponding 1,1-bis(substituted quinolin-2-yl)ferrocene derivatives 3p-t. The structures of compounds 3a-t were determined and characterized by infrared, 1H NMR, mass spectrometry, and elemental analysis. The crystal structures of 3e and 3q were determined by X-ray crystallography.

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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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New ferrocenyl compounds substituted by sulfur containing groups were synthesized leading to ferrocenyl-3H-1,2-dithiole-3-thiones and related compounds. The substituent of the ferrocene was a [3-thioxo-3H-1,2-dithiol]-4 or 5-yl, a [3-oxo-3H-1,2-dithiol]-4 or 5- yl or a [3-methylsulfanyl-3H-1,2-dithiolium]-4 or 5-yl cation group. Their anodic behavior was studied by cyclic voltammetry at a Pt electrode in aprotic solvent. All synthesized ferrocenes exhibited a one-electron reversible oxidation leading to the corresponding ferricinium cation. At low potential scan, the irreversible oxidation of 5-ferrocenyl-3H-1,2-dithiole-3-thione was observed and attributed to a dimerization involving the dithiolethione group. Redox potential of the reversible oxidation allowed the determination of the electronic effect of the 1,2-dithiole groups. The Hammett sigmap constants of the dithiole substituents were obtained from linear correlation between oxidation potentials and electronic effects. The results showed that the [3-thioxo-3H-1,2-dithiol]-5-yl and the [3-methylsulfanyl-3H-1,2-dithiolium]-5-yl cation groups were strong inductive electron withdrawing substituents characterized by sigmap values of 0.55 and 0.97, respectively.

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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 novel asymmetric 1,1?-ferrocene-derived Schiff base ligand has been prepared by the condensation reaction of 1,1?-diacetylferrocene with 2-aminopyridine and 2-aminothiazole. Its transition metal complexes of the type [M(L)]Cl2 and [M(L)(Cl2)] [M = Cu(II),Co(II) and Ni(II)] have been prepared and characterized by their physical, analytical and spectral data. The Cu(II) complex shows square-planar whereas the Co(II), Ni(II) and Zn(II) complexes show octahedral geometry.

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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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Thiomethoxychalcone-based ligands bis[3,3-bis(methylsulfanyl)]-1,1?- eta5-ferrocenyl-2-propen-1-one (L1), 3,3-bis(methylsulfanyl)-1-eta5-ferrocenyl-2-propen-1-one (L 2), and 3-methylsulfanyl-3-sulfanyl-1-eta5-ferrocenyl-2- propen-1-one (L3) have been synthesized on the ferrocene backbone by varying the number of chalcone arms and thiomethoxy substitutents. The single-crystal X-ray crystallographic analyses of all three ligands are reported in which crystals of L1 were obtained as both syn and anti conformers and showed the conformational freedom of the two cyclopentadienyl (Cp) units. L1-L3 are studied extensively toward their applicability in the colorimetric sensing of metal ions in solution. The solution-state study of mono- and bis(thiomethoxy)ferrocenylchalcone- functionalized ligands L1 and L2 showed selective colorimetric sensing for Hg2+ over Li+, Na+, Ca2+, Mg2+, Cr2+, Mn2+, Fe 2+, Co2+, Ni2+, Cu2+, Zn 2+, Cd2+, and Au3+ in acetonitrile. In both cases, a selective color change from orange to purple was observed with Hg 2+ and the resultant solution showed the appearance of a new peak at 565 nm (epsilon = 3920 M-1 cm-1) for L1 and 600 nm (epsilon = 1140 M-1 cm-1) for L2 in the UV/vis experiments. The UV/vis titration profiles of L1 and L 2 indicate the formation of 2:1 (L1/Hg2+) and 1:1 (L2/Hg2+) initial complexations in solution. On the other hand, L3 with thiomethoxy- and thiol-functionalized ferrocenylchalcone showed no appreciable color change with Hg2+ under the same experimental conditions. Attempts were made to isolate single crystals of the resulting purple solution obtained in the cases of L1 and L2 with Hg2+. In both cases, crystals suitable for a single-crystal X-ray diffraction study were isolated in very low yield by a layer diffusion technique. The single-crystal structural investigations demonstrated the formation of a sulfide-encapsulated mercury thiolate cuboctahedron cluster, [Hg8S(SCH3)12] 2+, upon a selective chemodosimetric desulfurization reaction between Hg2+ and L1 or L2. Cyclic voltammetric studies also support the Hg2+-induced cleavage of thiomethoxy groups.

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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 novel C[dbnd]N bond forming strategy based on oxo/imido heterometathesis between N-sulfinylamines and ketones, catalyzed by a well-defined silica-supported Ti imido complex, was applied to prepare a series of hardly accessible 1,1?-diacetylferrocene ketimines.

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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 structures adopted by a range of poly(pyrazolyl)borate complexes [ML2Tpx] [M = Rh, Ir; L2 = diene; Tp x = Bp? {dihydrobis(3,5-dimethylpyrazolyl)borate}, Tp? {hydrotris(3,5-dimethylpyrazolyl)borate}, Tp {hydrotris(pyrazolyl)borate}, B(pz)4 {tetrakis(pyrazolyl)borate}] have been investigated. Low steric hindrance between ligands in [Rh(eta-nbd)Tp] (nbd = norbornadiene), [Rh(eta-cod)Tp] (cod = cycloocta-1,5-diene) and [Rh(eta-nbd)Tp?] results in kappa3 coordination of the pyrazolylborate but [M(eta-cod)Tp?] (M = Rh, Ir) are kappa2 coordinated with the free pyrazolyl ring positioned above and approximately parallel to the square plane about the metal. All but the most sterically hindered Tp x complexes undergo fast exchange of the coordinated and uncoordinated pyrazolyl rings on the NMR spectroscopic timescale. For [Rh(eta-cod){B(pz)4}], [Rh(eta-dmbd)Tp?] (dmbd = 2,3-dimethylbuta-1,3-diene) and [Rh(eta-cod)TpPh] {TpPh = hydrotris(3-phenylpyrazolyl)borate} the fluxional process is slowed at low temperatures so that inequivalent pyrazolyl rings are observed. The bonding modes of the Tp? ligand (but not of other pyrazolylborate ligands) can be determined by 11B NMR and IR spectroscopy. The 11B chemical shifts (for a series of Tp? complexes) show the general pattern, kappa3 < -7.5 ppm < kappa2 and the nu(BH) stretch kappa3 > 2500 cm-1 > kappa2. The electrochemical behaviour of the pyrazolylborate complexes is related to the degree of structural change which occurs on electron transfer. One-electron oxidation of complexes with Tp?, Tp and B(pz)4 ligands is generally reversible although that of [Ir(eta-cod)Tp] is only reversible at higher scan rates and that of [Ir(eta-cod){B(pz)4}] is irreversible. Of the complexes with the more sterically hindered TpPh ligand, only [Rh(eta-nbd)TpPh] shows any degree of reversible oxidation. The ESR spectra of a range of Rh(ii) complexes show coupling to both 14N and 103Rh nuclei in most cases but what appears to be coupling to rhodium and one hydrogen atom, possibly a hydride ligand, for the oxidation product of [Rh(eta-nbd)TpPh]. The Royal Society of Chemistry 2008.

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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 have synthesized a novel disubslituted ferrocenyl compound [Fe(C 5H4CO(CH=CH)2C6H4NEt 2)2] (3) that displays a remarkable fluorescence quantum yield (1.1 × 10-1) in acetonitrile, and we have studied its capacity for calcium detection in depth using both electrochemical and optical techniques in this medium. The results of our NMR analysis reveal that the ligand-calcium interaction is CO-centered and that an uncommon equilibrium occurs between 3 and calcium triflate, involving five species of different stoichiometries. In contrast, our analysis of the UV-vis absorption data indicates that only three species of different stoichiometries are formed when calcium perchlorate is used with 3. Mass spectrometry measurements provide strong support for the formation of all these different species in solution. In addition, the electrochemical detection of calcium triflate by 3 leads to an irreversible FeII/ FeIII oxidation process with an unusual negative shift (-60 mV) caused by the nBu4NBF4 salt effect on the Ca2+-3 interaction process. Compound 3 can also be an original optical probe to detect calcium perchlorate over a wide range of salt concentration by UV-vis absorption spectroscopy. The most original and intriguing property of compound 3 is that it exhibits an unprecedented “multistep” fluorescence behavior upon addition of this salt.

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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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Reductive deoxygenation of acylferrocenes to the corresponding alkylferrocenes proceeded in excellent yields on utilizing a combination of sodium cyanotrihydroborate and boron trifluoride-diethyl ether.This method allows the synthesis of alkylferrocenes with functionalized tethers and is adaptable to large-scale preparations.

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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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A ligand, 1,1?-diacetylferrocene bis-2-furoylhydrazone (H 2Bafh), and its lanthanide [Ln(III)] complexes, [Ln(H 2Bafh)3]·(ClO4)3· nH2O [complexes A: Ln = La(III), Gd(III), Tm(III), Yb(III)], and [Ln(H2Bafh)Cl2]-Cl·nH2O [complexes B: Ln = Y(III), La(III), Nd(III), Gd(III), Tm(III)] were prepared and characterized by microanalyses, IR, 1H NMR, and UV-VIS spectra, molar conductivity, and TGA analyses.

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The effect of substituents in the Cp ligands on the electronic structure has been studied for the 1,1′-disubstituted ferrocenes Fe(CpX)2, with X = C2H5, OCH3, CN, COCH3, COOCH3, OOCCH3, CH2C6H5, or C6H5, by UV photoelectron spectroscopy and by CNDO/2 calculations.The energy gap between the 2E2g and 2A1g ion states, 0.36 eV in the parent ferrocene, is affected only by the COCH3 and COOCH3 substituents, which lower it to 0.22 and 0.28 eV, respectively.Splitting of e1u(?) level due to the lowering of the symmetry is the only effect observed in the photoelectron spectra.There is a strong conjugation between the phenyl and cyclopentadienyl ?-orbitals in 1,1′-diphenylferrocene.The changes in the a1g(d) ionization energy calculated by the DeltaSCF method using CNDO/2 total energies are in a good agreement with the experimental data.

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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