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Supercritical carbon dioxide in organometallic synthesis: Combination of sc-CO2 with Nafion film as a novel reagent in the synthesis of ethers from hydroxymethylmetallocenes

Metallocenyl carbinols FcCH2OH (1a) and RcCH2OH (1b) dissolved in sc-CO2 penetrate into the acidic Nafion film under 20 MPa and 80 or 35 C. After removal of pressure and leaving at room temperature, the crystals rapidly formed on the surface of the film, were identified as ethers McCH2OCH2Mc, Mc = Fc or Rc, by X-ray study. Mechanism of their formation is discussed.

Supercritical carbon dioxide in organometallic synthesis: Combination of sc-CO2 with Nafion film as a novel reagent in the synthesis of ethers from hydroxymethylmetallocenes

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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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Application of 1273-86-5, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1273-86-5, Name is Ferrocenemethanol, molecular formula is C11H3FeO. In a article£¬once mentioned of 1273-86-5

MOESSBAUER STUDIES ON FERROCENE COMPLEXES. III. STRUCTURE OF FERROCENYL CARBENIUM IONS

Moessbauer and NMR spectra are reported for ferrocenyl (Fc) carbenium ions, FcCH2+ (III+) and FcC+Me2 (II+) in frozen acidic media. 1H-NMR spectra showed no evidence of Fe-H bonded species.Moessbauer parameters for II+ were identical within experimental error to those obtained for the carbenium ion precursors and to ferrocene itself, whereas quadrupole splittings for III+ were significantly larger.The results for the latter species are interpreted in terms of stabilisation via orbital overlaps with the central iron atom.

MOESSBAUER STUDIES ON FERROCENE COMPLEXES. III. STRUCTURE OF FERROCENYL CARBENIUM IONS

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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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(eta6-Arene)tricarbonylchromium and ferrocene complexes linked to binaphthyl derivatives

Palladium-catalyzed coupling reactions of 6,6?-dihydroxyboron-2, 2?-dimethoxy-1,1?-binaphthyl 5g and chloroarenetricarbonylchromium complexes 6a – c afforded complexes 7a – c with the binaphthyl residue directly linked to the (eta6-arene)tricarbonylcriromium entity. Coupling reactions of 2,2?-dimethoxy, 3,3?diodo, and 6,6?-diodo-1, 1?-binaphthyl 3h and 5h with ethynylarenetricarbonylchromium derivatives 6d – f and ethynylferrocene 9 yielded binaphthyl compounds linked to arenetricarbonylchromium and feirocenyl derivatives 8a – c, 11a – c, 10, and 12 through a triple bond. Condensation of 2,2?-dimethylrriethoxy, 3-formyl, 1,1?-binaphthyl 2a with (eta6-phenyl) methyltriphenylphosphonium tricarbonylchromium 13 and ferrocenylmethyltriphenylphosphonium 18 gave binaphthyl compounds linked to arenetricarbonylchromium and ferrocenyl derivatives 14 and 19, respectively, through a double bond. X-ray analyses of the dinuclear chromium complex 8a and of the mononuclear chromium complex 17-Z are described.

(eta6-Arene)tricarbonylchromium and ferrocene complexes linked to binaphthyl 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 highly sensitive and stable glucose biosensor using thymine-based polycations into laponite hydrogel films

A series of glucose bioelectrodes were prepared by glucose oxidase (GOx) immobilization into laponite hydrogel films containing DNA bioinspired polycations made of vinylbenzyl thymine (VBT) and vinylbenzyl triethylammonium chloride (VBA) with general formulae [(VBT)m(VBA)n] 25n+ with m=0, 1 and n=2, 4, 8, deposited onto glassy carbon electrode. The bioelectrodes were characterized by chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy. Results indicated that the electrochemical properties of the laponite hydrogel films were largely improved by the incorporation of thymine-based polycations, being proportional to the positive charge density of the polycation molecule. After incorporation of glucose oxidase, the sensitivity of the bioelectrode to glucose increased with the positive charge density of the polycation. Additionally, the presence of the vinylbenzyl thymine moiety played a role in the long-term stability and reproducibility of the bioelectrode signal. As a consequence, the [(VBT)(VBA)8]258+ was the most appropriate polycation for bioelectrode preparation and glucose sensing, with a specific sensitivity of se=176 mA mmol-1 L cm-2 U-1, almost two-order of magnitude larger than other laponite immobilized GOx bioelectrodes reported elsewhere. These features were confirmed by testing the bioelectrode for a selective determination of glucose in powder milk and blood serum samples without interference of either ascorbic or uric acids under the experimental conditions. The present study demonstrates the suitability of DNA bioinspired water-soluble polycations [(VBT)m(VBA)n]25n+ for enzyme immobilization like GOx into laponite hydrogels, and the preparation of highly sensitive and stable bioelectrodes on glassy carbon surface.

A highly sensitive and stable glucose biosensor using thymine-based polycations into laponite hydrogel films

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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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Synthetic Route of 1273-86-5, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1273-86-5, Name is Ferrocenemethanol, molecular formula is C11H3FeO. In a article£¬once mentioned of 1273-86-5

Nitro-imidazoles in ferrocenyl alkylation reaction. Synthesis, enantiomeric resolution and in vitro and in vivo bioeffects

Ferrocenylalkyl nitro-imidazoles (4a-h, 5a-h) were prepared via the regiospecific reaction of the alpha-(hydroxy)alkyl ferrocenes, FcCHR (OH) (1a?h; Fc = ferrocenyl; R = H, Me, Et, Pr, i-Pr, Ph, ortho-Cl-Ph, ortho-I-Ph), with nitro-imidazoles in aqueous organic medium (H2O-CH2Cl2) at room temperature in the presence of HBF4, within several minutes in good yields. X-ray structural data for racemic (R,S)-1-N-(benzyl ferrocenyl)-2-methyl-4-nitroimidazole (5f) were determined. The resulting enantiomers were resolved into enantiomers by analytical HPLC on modified amylose or cellulose chiral stationary phases. The viabilities of 4b, 4d, 5b, 5c in vitro, and in experiments in vivo antitumor effects of 1-N-ferrocenylethyl-4-nitroimidazole (4b) against murine solid tumor system Ca755 carcinoma were evaluated.

Nitro-imidazoles in ferrocenyl alkylation reaction. Synthesis, enantiomeric resolution and in vitro and in vivo bioeffects

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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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Time-dependent behavior of cation transport through cellulose acetate-cationic polyelectrolyte membranes

Cation transport through a cellulose acetate-poly(N,N-dimethylaminoethyl methacrylate) membrane (CA:PDMAEMA) was studied with scanning electrochemical microscope (SECM) and the thickness increase of the membrane was monitored with ellipsometry. Upon addition of the polyelectrolyte PDMAEMA, the permeability of the probe cation (ferrocenium methanol, FcMeOH) was increased as much as 40-fold. Soaking membranes in an electrolyte solution doubled the permeability in plain CA membranes, whereas for PDMAEMA containing membranes the opposite was observed and the permeability was reduced by 20?40%. This time-dependent behavior is shown to be a result of the presence of PDMAEMA within the membrane matrix, thus providing an interesting platform for controllable membrane permeability.

Time-dependent behavior of cation transport through cellulose acetate-cationic polyelectrolyte membranes

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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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Redox active ferrocene-modified pyrimidines and adenine as antitumor agents: Structure, separation of enantiomers, and inhihibition of the DNA synthesis in tumor cells

The structures, electrochemical properties, enantiomeric separation of ferrocenyl (alkyl)pyrimidines and ferrocenyl(ethyl)adenine and their effects on the DNA synthesis in tumor cells were studied. Enantiomeric mixtures were separated by HPLC on modified cellu lose as the chiral selector. The electrochemical properties of compounds were studied by cyclic voltammetry. All compounds have reversible singleelectron redox transition in the region of 0.52-0.60 V, which belongs to ferrocene-ferrocenium with a positive shift compared to ferrocene (0.52 V). The molecular structure of 1N (ferrocenylbenzyl)5iodocytosine was studied by X-ray diffraction. 1-N (Ferrocenylethyl)adenine was studied for ability to inhibit the DNA synthesis in the human ovarian cancer cell culture by the 3H thymidine test.

Redox active ferrocene-modified pyrimidines and adenine as antitumor agents: Structure, separation of enantiomers, and inhihibition of the DNA synthesis in tumor cells

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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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Structure-activity relationship of trifluoromethyl-containing metallocenes: Electrochemistry, lipophilicity, cytotoxicity, and ROS production

We report the synthesis of trifluoromethylated metallocenes (M=Fe, Ru) and related metal-free compounds for comparison of their biological properties with the aim to establish structure-activity relationships toward the anti-proliferative activity of this compound class. All new compounds were comprehensively characterized by NMR spectroscopy (1H, 13C, 19F), mass spectrometry, IR spectroscopy, and elemental analysis. A single-crystal X-ray structure was obtained on the Ru derivative, 1-(1-hydroxy-1-hexafluoromethylethyl)ruthenocene (3). The cytotoxicity of all compounds was tested on MCF-7, HT-29, and PT-45 cells, and IC50 values as low as 12 muM were observed. Both the metallocene moiety and the hydroxy function are crucial for cytotoxicity. In addition, the activity decreased sharply even if only one trifluoromethyl group was replaced with a methyl group. Electrochemical investigations by cyclic voltammetry revealed that all CF3-containing compounds are harder to oxidize than the unsubstituted metallocenes. Moreover, log-P determination by RP-HPLC showed the fluorinated derivatives to have higher lipophilicity, with log-P values up to 4.6. At the same time, the generation of reactive oxygen species (ROS) in Jurkat cells by these compounds was investigated by flow cytometry. Strong ROS production was shown exclusively for the bis-CF3 derivative 1-(1-hydroxy-1-hexafluoromethylethyl)ferrocene (1) after 6 and 24 h. Also on the Jurkat cell line, only compound 1 strongly induces necrosis after 24 and 48 h, as shown by annexin V/propidium iodide staining. No induction of apoptosis was observed. We propose that compound 1 is more efficiently incorporated into cancer cells relative to all other derivatives, causing significant induction of oxidative stress within the cell, which ultimately leads to cell death. Fluorinated oxidizers: A series of trifluoromethyl-containing metallocenes was synthesized to carry out SAR determinations. All compounds were tested for cytotoxic effects against a range of cancer cell lines, ROS production, electrochemical behavior, lipophilicity, and their capacity to induce apoptosis/ necrosis. Cytotoxicity assays underscore the crucial role of the metallocene moiety, CF3 groups, and the OH function for anti-proliferative effects.

Structure-activity relationship of trifluoromethyl-containing metallocenes: Electrochemistry, lipophilicity, cytotoxicity, and ROS production

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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 REINVESTIGATION OF THE MASS SPECTRA OF SUBSTITUTED FERROCENES: ACCURATE FRAGMENTATION PATHWAYS AND IONIC STRUCTURES BY ANALYSIS OF METASTABLE ION SPECTRA

The mass spectra of substituted ferrocenes have been reinvestigated making intensive use of the metastable ions.The observed primary fragmentations of the molecular ions are different in some respects from those previously postulated.The study of the metastable ions characteristics of the ions at m/z 186 and m/z 121 indicates that their structures are independent of their precursor ions.

A REINVESTIGATION OF THE MASS SPECTRA OF SUBSTITUTED FERROCENES: ACCURATE FRAGMENTATION PATHWAYS AND IONIC STRUCTURES BY ANALYSIS OF METASTABLE ION SPECTRA

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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, structure and redox potentials of biologically active ferrocenylalkyl azoles

The syntheses, structures, electrochemical properties of the series of ferrocenylalkyl azoles, FcAlkAz, as well as the antitumor activity of ferrocenylmethyl benzimidazole (8) have been studied. Above mentioned compounds were investigated by the method of cyclic voltametry. All of them exhibited a reversible one-electron oxidation-reduction wave owing to the ferrocene-ferrocenium redox couple with a positive shift (0.50-0.65 V) compared with that of ferrocene (0.42 V). The X-ray determination of molecular structures of 1-(ferrocenylmethyl)imidazole (4), 1-(ferrocenylbenzyl)imidazole (7) and 1-(ferrocenylmethyl)bezimidazole (8) was carried out. Compound 4 with imidazolyl substituent was found to be present in N-protonated form. Antitumor activity of 1-(ferrocenylmethyl)benzimidazole (8) against some solid tumor models such as adenocarcinoma 755 (Ca755), melanoma B16 (B16) and Lewis lung carcinoma was studied. The antitumor activity of compound 8 was compared with cisplatin effectiveness against some experimental tumor systems.

Synthesis, structure and redox potentials of biologically active ferrocenylalkyl azoles

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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