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Synthesis, characterization and anticancer activity of La(III), Ce(III), Pr(III) and Gd(III) complexes of 1,1?-Bis(Z)-N-ethyldiene-5-methylthiazol-2-amine ferrocene

Condensation of 1,1?-diacetyl ferrocene with 2-amino-5-methylthiazole in 1: 2 molar ratio yields a ferrocenyl Schiff base ligand 1,1?-bis(Z)-N-ethyldiene-5-methylthiazol-2-amine ferrocene (L). This ligand forms 1:1 complexes with La(III), Ce(III), Pr(III) and Gd(III) nitrate in a good yield. Characterization of the ligand and complexes were carried out using infrared, nuclear magnetic resonance, mass spectra, electronic absorption, magnetic susceptibility, molar conductivity and elemental analysis. The cytotoxicity and in vitro anticancer evaluation of the ligand and its complexes have been assessed against four different human tumor cell lines (MCF-7, HepG2, A549 and HCT116). The results revealed that the prepared compounds exert their actions in HepG2 and MCF-7 through inhibition of the activity of both urokinase and histone deacetylase (HDAC). Pr-complex revealed promising anticancer activity compared to the activity of the commonly used anticancer drug, doxorubicin.

Synthesis, characterization and anticancer activity of La(III), Ce(III), Pr(III) and Gd(III) complexes of 1,1?-Bis(Z)-N-ethyldiene-5-methylthiazol-2-amine ferrocene

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Influence of Hartree-Fock exchange on the calculated Moessbauer isomer shifts and quadrupole splittings in ferrocene derivatives using density functional theory

Influence of molecular geometry, type of exchange-correlation functional, and contraction scheme of basis set applied at the iron nuclei have been tested in the calculation of 57Fe Moessbauer isomer shifts and quadrupole splittings for a wide range of ligand types, as well as oxidation and spin states, in inorganic and organometallic systems. It has been found that uncontraction of the s-part of Wachter’s full-electron basis set at the iron nuclei does not appreciably improve the calculated isomer shifts. The observed correlations for all tested sets of geometries are close to each other and predominantly depend on the employed exchange-correlation functional with B3LYP functional being slightly better as compared to BPW91. Both hybrid (B3LYP) and pure (BPW91) exchange-correlation functionals are suitable for the calculation of isomer shifts in organometallic compounds. Surprisingly, it has been found that the hybrid B3LYP exchange-correlation functional completely fails in accurate prediction of quadrupole splittings in ferrocenes, while performance of the pure BPW91 functional for the same systems was excellent. This observation has been explained on the basis of relationship between the amount of Hartree-Fock exchange involved in the applied exchange-correlation functional and the calculated HOMO-LUMO energy gap in ferrocenes. On the basis of this explanation, use of only pure exchange-correlation functionals has been suggested for accurate prediction of Moessbauer spectra parameters in ferrocenes.

Influence of Hartree-Fock exchange on the calculated Moessbauer isomer shifts and quadrupole splittings in ferrocene derivatives using density functional theory

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A double-helix generated from a ferrocenyl-thiosemicarbazato metallo-synthon and its novel hydrogen-bonding cavities

A double helical architecture generated from a readily prepared ferrocenyl-containing bisthiosemicarbazone ligand is described together with its application to the self-assembly of novel supramolecular hydrogen-bonding cavities.

A double-helix generated from a ferrocenyl-thiosemicarbazato metallo-synthon and its novel hydrogen-bonding cavities

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Synthesis of N?-substituted derivatives of 5-(4-methylphenyl)isoxazole-3-carbohydrazonamide

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.

Synthesis of N?-substituted derivatives of 5-(4-methylphenyl)isoxazole-3-carbohydrazonamide

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Preparation of mannitol-based ketal-linked porous organic polymers and their application for selective capture of carbon dioxide

Four kinds of mannitol-based ketal-linked porous organic polymers (MKPOPs) were successfully synthesized through condensation reaction between aromatic acetyl monomers and mannitol, catalyzed by p-toluenesulfonic acid. The structure of resulting polymers was confirmed by Fourier transform infrared and solid-state 13C nuclear magnetic resonance spectrum measurements. The porosities of MKPOPs were investigated by gas adsorption experiments and the results indicate high carbon dioxide uptake (up to 11.5 wt% at 273 K and 1.0 bar) for MKPOPs due to the predominant microporous and hydroxyl-rich structures. Remarkably, MKPOPs exhibit excellent selective adsorption performances for carbon dioxide over methane (9.9-14.2, IAST at 273 K and 1.0 bar). These studies are of significant importance for MKPOPs and their potential application in selective gas adsorption.

Preparation of mannitol-based ketal-linked porous organic polymers and their application for selective capture of carbon dioxide

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Synthesis of alpha-arylalkylferrocenes through cesium fluoride-promoted coupling of arylboronic acids with N-tosylhydrazones

A cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted alpha-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C?B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the alpha-arylalkylferrocenes compounds were also obtained on a multi-gram scale.

Synthesis of alpha-arylalkylferrocenes through cesium fluoride-promoted coupling of arylboronic acids with N-tosylhydrazones

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A highly efficient synthesis of optically active ferrocenylethylamines via hydride reduction of chiral ferrocenylketimines

Due to using (R)- or (S)-alpha-methylbenzylamine as a chiral auxiliary, and low-temperature regime for reduction of the intermediate ferrocenyl-mono- or 1,1?-bis-ketimines, the corresponding secondary mono- or 1,1?-bis-amines were prepared with high diastereoselectivity. Removal of the alpha-methylbenzyl group afforded the optically active primary mono- and bis-ferrocenylethylamines in high yields. The absolute configuration of (R,R)-3a and (S,S)-3b was determined by X-ray single crystal diffraction. We have developed an efficient and highly stereoselective synthesis of the chiral mono- and bis-ferrocenylamines via sodium borohydride reduction, followed by reductive cleavage of the alpha-methylbenzyl moiety using 5% Pd/C and HCOONH 4. The selectivity was up to 99% de. Copyright

A highly efficient synthesis of optically active ferrocenylethylamines via hydride reduction of chiral ferrocenylketimines

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1,1′-Diacetylferrocenebis(5-phenyl-1,3-oxazol-2-ylcarbonyl)hydrazone and its complexes

A new heterocyclic ferrocene derivative, 1,1′-diacetylferrocenebis(5-phenyl-1,3-oxazol-2-ylcarbonyl)hydrazone (H2Dfoh) and its coordination complexes, [M2(Dfoh)¡¤(OAc)2]¡¤nH2O [(M = Cu(II), Ni(II), Co(II), Cd(II), Pb(II), Mn(II)], were prepared by reacting H2Dfoh with the metal acetates and were characterized by elemental analyses, molar conductivities, IR, 1H NMR, UV spectra and thermal analyses. H2Dfoh appears to act as a bidentate ligand, coordinating to two metal atoms through the azomethine nitrogen and enolic oxygen atoms. OAc- coordinates to the metals as a symmetric bidentate ligand.

1,1′-Diacetylferrocenebis(5-phenyl-1,3-oxazol-2-ylcarbonyl)hydrazone and its complexes

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Construction of five- and six-membered heterocycles on both Cp rings of the ferrocene moiety of alpha-oxoketene-S,S-acetal and beta-oxodithioester via heteroaromatic annulation

1,1?-Bis(1,1-dimethylsulfanyl-3-oxo-1-propene)ferrocene and 1,1?-Bis(methyl-3-hydroxy-prop-2-ene-dithioate)ferrocene have been shown to be useful three-carbon synthons for the efficient synthesis of hitherto unreported and synthetically demanding Fc-heterocycles. Five-membered (pyrazole, isoxazole, and thiophene) and six-membered (pyrimidine, coumarin, and quinoline) heterocycles have been constructed on both Cp rings of the ferrocene matrix via regioselective heteroaromatic annulation. The Royal Society of Chemistry.

Construction of five- and six-membered heterocycles on both Cp rings of the ferrocene moiety of alpha-oxoketene-S,S-acetal and beta-oxodithioester via heteroaromatic annulation

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Selective functionalization of ferrocenyl compounds using a novel solvent free synthetic method for the preparation of bioactive unsymmetrical ferrocenyl derivatives

A novel solvent free synthetic method has been designed by using rice husk ash (RHA) as solid support for the selective functionalization of ferrocenyl derivatives and described the synthesis of a 1,1?-unsymmetrically bi-functionalized ferrocenyl compounds for their biological evaluation. Single crystal X-ray structural evaluation showed some interesting intra-molecular hydrogen bonding interactions across the chains of the ferrocenyl molecule, while DFT calculation revealed the significance of the orientation between the two cyclopentadienyl rings for the hydrogen bonding interaction. Redox and antibacterial properties have been studied to understand the electronic and biological effect of different hydrazone system and their potential for future application.

Selective functionalization of ferrocenyl compounds using a novel solvent free synthetic method for the preparation of bioactive unsymmetrical ferrocenyl derivatives

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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