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The synthesis and characterisation of heterosubstituted aminoferrocenes

The synthesis of 1-bromo-1?-aminoferrocene is reported using a simple synthetic methodology. This compound serves as a useful precursor to other heterosubstituted aminoferrocenes. For example, (1?-amino)ferrocenecarboxylic acid has been obtained and is conveniently isolated in its C-protected form by lithiation of 1-bromo-1?-aminoferrocene, quenching with solid carbon dioxide and esterification of the resulting carboxylate with methanolic HCl. The new ligand 1-diphenylphosphino-1?-aminoferrocene has also been obtained using a similar methodology.

The synthesis and characterisation of heterosubstituted aminoferrocenes

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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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Synthesis and physico-analytical studies of some novel ferrocenyl Schiff base derivatives

A series of ferrocenyl Schiff base derivatives was synthesized by condensation reactions of 1,1?-ferrocenedicarboxaldehyde and aromatic amines containing long chain alkyl groups as free ends which were characterized by their physical properties, elemental, FTIR, 1H NMR, 13C NMR spectral and thermal analysis. The thermal behaviour of the synthesized compounds was studied by differential scanning calorimetry (DSC) which revealed that these compounds may exhibit mesomorphic properties. The DSC results of aromatic amines and ferrocenyl Schiff bases were compared to study the effects of structure, i.e. rigid core and terminal chain length, on the phase transition behaviour.

Synthesis and physico-analytical studies of some novel ferrocenyl Schiff base 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

 

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A new facile two-step synthetic procedure of 1,1′-diaminoferrocene

1,1′-Diaminoferrocene (3) was conveniently synthesized by employing a Gabriel synthesis in two steps starting from 1,1′-dibromoferrocene (1). Compound 1 was reacted with 2.5 equivalents of phthalimide in the presence of Cu 2O using 4-picoline as a solvent to give 1,1′-diphthalimidoferrocene (2) in a moderate yield. Hydrazinolysis of 2 in EtOH afforded 3 in good yields of ca. 70%. The subsequent reaction of 3 with two equivalents of ethyloxalyl chloride in THF gave the diethyl ester of N,N’-ferrocenylene bis(oxamic acid) (1,1′-fcbaH2Et2, 4). The solution obtained by treating 4 with two equivalents of n-Bu4NOH in H2O was added to a solution of Pd(AcO)2 in THF to give the palladium complex [n-Bu 4N]2[Pd(1,1′-fcba)] (5) in ca. 80% yield. The compounds 24 were characterized by 1H, 13CNMR and IR spectroscopy as well as elemental analysis and the heterobinuclear complex 5 by 1H NMR and IR spectroscopy, elemental analysis and by a single-crystal X-ray diffraction study.

A new facile two-step synthetic procedure of 1,1′-diaminoferrocene

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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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Efficient conversion of primary azides to aldehydes catalyzed by active site variants of myoglobin

The oxidation of primary azides to aldehydes constitutes a convenient but underdeveloped transformation for which no efficient methods are available. Here, we demonstrate that engineered variants of the hemoprotein myoglobin can catalyze this transformation with high efficiency (up to 8500 turnovers) and selectivity across a range of structurally diverse aryl-substituted primary azides. Mutagenesis of the ‘distal’ histidine residue was particularly effective in enhancing the azide oxidation reactivity of myoglobin, enabling these reactions to proceed in good to excellent yields (37-89%) and to be carried out at a synthetically useful scale. Kinetic isotope effect, isotope labeling, and substrate binding experiments support a mechanism involving heme-catalyzed decomposition of the organic azide followed by alpha hydrogen deprotonation to generate an aldimine which, upon hydrolysis, releases the aldehyde product. This work provides the first example of a biocatalytic azide-to-aldehyde conversion and expands the range of non-native chemical transformations accessible through hemoprotein-mediated catalysis.

Efficient conversion of primary azides to aldehydes catalyzed by active site variants of myoglobin

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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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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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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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Synthesis of multifunctional aza-substituted ruthenocene derivatives displaying charge-transfer transitions And selective Zn(II) ions sensing properties

The synthesis, electrochemical, electronic, and cation sensing properties of multinuclear nitrogen-rich [2.2]- and [3.3]-mixed ferrocene and ruthenocene metallocenophanes are presented. Structural features of these new structural motifs are that the two redox organometallics fragments are linked by unsaturated nitrogen functionalities, for example, carbodiimide or aldimine, as well as the nitrogen atom is directly attached to the ruthenocene unit. The key bis(iminophosphorane) 3 is readily prepared by the Staudinger reaction between triphenylphosphine and 1,1?-diazidoruthenocene 2, which has been prepared from 1,1?- dilithioruthenocene and 2,4,6-trisopropylbenzenesulfonyl azide (trisyl azide). Subsequent aza-Wittig reactions of 3 with the appropriate carbonyl or thiocarbonyl compounds provided the opened ruthenocenebased isothiocyanate 4, and the closed carbodiimide 5 and aldimines 6 and 7. Spectroelectrochemical studies of carbodiimide 5 and aldimine 7 revealed the presence of low-energy bands in the near-IR region in the partially oxidized forms, at 1029 and 1481 nm, respectively, which indicate the existence of intramolecular charge transfer between the iron and the ruthenium centers. The experimental data and conclusions are supported by DFT computations. Moreover, the aldimine 7 behaves as a selective colorimetric chemosensor molecules for Zn2+ ions. The low-energy (LE) band of the absorption spectrum of this compound is red-shifted by 99 nm, only in the presence of Zn2+ ions. This change in the absorption spectrum is accompanied by a dramatic color change, which allows the potential for “naked eye” detection.

Synthesis of multifunctional aza-substituted ruthenocene derivatives displaying charge-transfer transitions And selective Zn(II) ions sensing properties

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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 general metal-free route towards the synthesis of 1,2,3-triazoles from readily available primary amines and ketones

An unprecedented approach that enables the direct and selective preparation of 1,5-disubstituted 1,2,3-triazoles from abundantly available building blocks such as primary amines, enolizable ketones and 4-nitrophenyl azide as a renewable source of dinitrogen via an organocascade process has been developed. Furthermore, this efficient methodology also enables the synthesis of fully functionalized and fused N-substituted heterocycles.

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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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Synthesis, crystal structures, electrochemical properties, and complexation of ferrocene-based compounds: 1,2-bis(dimethyldithiocarbamate)ferrocene and 1,2-bis(benzothiazol-2-ylthio)ferrocene

Ferrocene-based metalloligands have various applications in material sciences due to their stability in air and redox active properties. Two ferrocene-based compounds, 1,2-bis(dimethyldithiocarbamate)ferrocene (1) and 1,2-bis(benzothiazol-2-ylthio)ferrocene (2), were synthesized from 1,1?-dibromoferrocene and the corresponding disulfides via two steps. The reaction of 1 with PdCl2(PhCN)2 formed a 1:1 metal:ligand complex, [PdCl2(1)]. Compounds 1, 2, and [PdCl2(1)] were structurally characterized by single-crystal X-ray diffraction, and their redox potentials were measured by cyclic voltammetry. Two pseudopolymorphs, ethanol-solvated 1(C2H5OH)0.33 and non-solvated 1, were obtained by recrystallization from ethanol. The Xray structure of [PdCl2(1)] showed that the Pd(II) center was chelated by 1 with two thioketone sulfur atoms; 1 showed two irreversible oxidationpeaks at 0.17 and 0.41 V (vs. Fe(Cp)2/Fe(Cp)2+), corresponding to oxidation of the two substituents and ferrocene, respectively. Conversely, 2 showed a quasi-reversible redox potential at E1/2 = 0.40 V, attributable to the ferrocene moiety. [PdCl2(1)] showed two irreversible oxidation peaks at 0.48 and 0.64 V and a reduction peak at 0.52 V (vs. Fe(Cp)2/Fe(Cp)2+).

Synthesis, crystal structures, electrochemical properties, and complexation of ferrocene-based compounds: 1,2-bis(dimethyldithiocarbamate)ferrocene and 1,2-bis(benzothiazol-2-ylthio)ferrocene

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Reference£º
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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Pronounced effects of crystal structures on intramolecular electron transfer in mixed-valence biferrocenium cations: Structural, EPR, and 57Fe Moessbauer characteristics

Crystallographic properties play an important role in controlling the rate of electron transfer in mixed-valence 1?,1?-disubstituted-biferrocenium triiodide salts. The X-ray structure of neutral 1?,1?-dinaphthylmethylbiferrocene has been determined at 298 K. The corresponding mixed-valence 1?,1?-dinaphthylmethylbiferrocenium triiodide exhibits two crystalline morphologies at 298 K. Dark crystals, formed when a CH2Cl2 solution of triiodide salt was allowed to evaporate slowly, crystallize in space group P1. Dark crystals, obtained when a layer of hexane was allowed to slowly diffuse into a CH2Cl2 solution of triiodide salt, crystallize in monoclinic space group P21/n. The observations of the structural characteristics of 1?,1?-dinaphthylmethylbiferrocenium triiodide are also consistent with our Moessbauer studies. The cation with space group P1 shows two doublets in the variable-temperature Moessbauer spectra at temperatures below 100 K. An increase of temperature causes the two doublets to move together, resulting in an average-valence doublet at 130 K. At 300 K, the spectrum of this sample shows a single doublet which is characteristic of a valence-detrapped cation in which the electron-transfer rate exceeds ?108 s-1. On the other hand, the cation with P21n phase exhibits a Moessbauer spectrum characteric of a valence-trapped cation at 300 K. Obviously, the intramolecular electron-transfer rate is quite sensitive to environment perturbations caused by different crystal packing arrangements. At 77 K, the EPR spectrum of cation with P1 phase is clearly a typical axial-type spectrum with g? = 3.16 and g? = 1.91. Surprisingly, the EPR spectrum of the cation with P21/n phase consists of two g? signals (3.67 and 2.85) and two g? signals (2.01 and 1.79). We suggest that the origin arises from the interaction of spin-spin exchange resulting from a dipole-dipole interaction that develops between cations. The syntheses, characterizations, and physical properties of mixed-valence 1?,1?-di(4-biphenylmethyl)biferrocenium and 1?,1?-di(9-anthracenylmethyl)biferrocenium triiodide salts are also described.

Pronounced effects of crystal structures on intramolecular electron transfer in mixed-valence biferrocenium cations: Structural, EPR, and 57Fe Moessbauer characteristics

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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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1,1?-homodisubstituted ferrocenes containing adenine and thymine nucleobases: Synthesis, electrochemistry, and formation of H-bonded arrays

Four organometallic nucleobases have been prepared and characterized, each consisting of a disubstituted ferrocene unit connected through either a conjugated or saturated linker group to adenine or thymine nucleobases. Their assembly behavior has been studied in the solid state via X-ray crystallography, revealing intermolecular H-bonded arrays. The electrode potentials in DCM are strongly dependent upon the nature of the linker group between the ferrocene unit and the nucleobase.

1,1?-homodisubstituted ferrocenes containing adenine and thymine nucleobases: Synthesis, electrochemistry, and formation of H-bonded arrays

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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