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Rigid N-(substituted)-2-aza-[3]-ferrocenophanes L1 and L2 were easily synthesized from 1,1 -dicarboxyaldehydeferrocene and the corresponding amines. Ligands L1 and L2 were characterized by 1H NMR, 13C NMR and single-crystal X-ray crystallography. The coordination abilities of L1 and L2 with metal ions such as Cu2+, Mg2+, Ni2+, Zn2+, Pb2+ and Cd2+ were evaluated by cyclic voltammetry. The electrochemical shift (DeltaE1/2) of 125 mV was observed in the presence of Cu2+ ion, while no significant shift of the Fc/Fc + couple was observed when Mg2+, Ni2+, Zn 2+, Pb2+, Cd2+ metal ions were added to the solution of L1 in the mixture of MeOH and H2O. Moreover, the extent of the anodic shift of redox potentials was approximately equal to that induced by Cu2+ alone when a mixture of Cu2+, Mg2+, Ni2+, Zn2+, Pb2+ and Cd2+ was added to a solution of L1. Ligand L1 was proved to selectively sense Cu2+ in the presence of large, excessive first-row transition and late-transition metal cations. The coordination model was proposed from the results of controlled experiments and quantum calculations.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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A series of ferrocenyl derivatives of the two non steroidal antiandrogens flutamide and bicalutamide have been prepared. Ferrocenyl bicalutamide complexes were initially synthesized in their racemic forms, and subsequently prepared as pure (R) and (S) enantiomers, and their structure was determined by X-ray crystallography. Most of the complexes retain a modest affinity for the androgen receptor and show an antiproliferative effect on both hormone-dependent (LNCaP) and -independent (PC-3) prostate cancer cells. Ferrocenyl derivatives of bicalutamide are the most cytotoxic (IC50 values on PC-3 around 15 muM); however, they are less potent than the ferrocenyl derivatives of ethynyltestosterone or nilutamide (IC50 around 5 muM).

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The metallocene cation complex [Cp*2ZrCH3] +[B(C6F5)4]- inserts the phosphino-substituted alkyne Ph-Ci – 1/4C-PPh2 into the [Zr]-CH3 bond to form the internally phosphane-stabilized cation [Cp*2Zr-C(=CMePh)PPh2]+ (10). Complex 10 adds alkyl isocyanides as well as pivalonitrile at a lateral site at the bent metallocene wedge with retention of the Zr-P bond. Complex 10 acts as a reactive frustrated Lewis pair toward heterocumulenes, undergoing Zr+/P addition reactions to the carbonyl groups of an alkyl isocyanate and of carbon dioxide to form the respective five-membered metallaheterocyclic adducts 13 and 14. With mesityl azide complex 10 undergoes a Zr+/P FLP N,N-addition reaction at the terminal azide nitrogen atom to form the four-membered FLP cycloadduct 15. The Zr+/P FLP is a reactive hydrogen activator. In a stoichiometric reaction it generates a hydridozirconocene cation that subsequently serves as a hydrogenation catalyst for various olefinic or acetylenic substrates. The Zr+/P pair 10 undergoes selective 1,4-addition reactions to conjugated enones and to a conjugated ynone to give the corresponding seven-membered metallacyclic Zr+/P FLP addition products. Many compounds of this study were characterized by X-ray diffraction.

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Ferrocenyl(alkyl)azoles were synthesized in high yields by interaction of alpha-ferrocenylcarbinoles with azoles in aqueous-organic in the presence of HBF4 or by interaction of alpha-ferrocenylcarbinoles with N,N?-carbonyldiimidazole, N,N?-thionyldiimidazole, N,N?-thionyldibenzimidazole in boiling dichloromethane. The resulting enantiomers of ferrocenyl(alkyl) azoles and some carbinoles were separated using HPLC on silica bonded chiral stationary phases based on cyclodextrins and modified cellulose.

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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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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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Mono-and disubstituted ferrocenes react with excess mercuric acetate (at least eight or nine equivalents) to afford highly insoluble mixtures of polymercurated ferrocenes. In the case of 1,1?-dimethylferrocene, the mercurated product is composed of minor amounts of the octamercurated and hexamercurated ferrocenes, with the heptamercurated ferrocene being the major product. This analysis is based upon results of chlorination and bromination studies of the mercurated species. It is proposed that exhaustive mercuration fails due to the extreme insolubility of the higher mercurated products.

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Saffron is an edible spice with highly appreciated sensory and antioxidant properties. One of the most representative redox species found in saffron extracts is crocin, whose content is used to evaluate the quality and value of the resulting spice. In this study, a voltammetry method based on the direct detection of crocin at a bare glassy carbon electrode is presented. The principle of the method is based on the monitoring of the anodic wave exhibited by crocin (0.1?1.0 mM) after its mixing with the azo radical initiator AAPH (20 mM) in ethanol:acetonitrile (1 : 1) solution. The decay rate of the anodic peak (E=+434 mV vs. Ag/Ag+), as a result of the consumption of crocin by AAPH, was used as index of the hydrogen transfer capacity and, thus, of its antioxidant activity. With a decay rate of k=0.02 h?1, crocin exhibits only a weak antioxidant activity in comparison with tocopherols (k=0.13 h?1), but still sufficient to protect against the oxidation of safranal, a further redox species found in saffron extracts and mainly responsible for its flavor. The proposed approach was finally applied to discriminate saffron extract samples from different geographical origins. The proposed approach is suitable to characterize the quality of saffron extracts and estimate its antioxidant properties.

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The enantioselective, intermolecular hydroallylation of vinylarenes employing allylic phosphate electrophiles has been achieved through a copper hydride catalyzed process. The protocol described herein can be applied to a diverse set of vinylarene substrates and allows for the installation of the parent allyl group as well as a range of 2-substituted allylic fragments.

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A carbon paste electrode was modified with the ionic liquid 1-methyl-3-octyl imidazolium hexafluorophosphate and it was applied for study the electrocatalytic oxidation and voltammetric determination of the drug sulfamethazine. The developed modified electrode was characterized using cyclic voltammetry and scanning electron microscopy. The oxidation of sulfamethazine at the surface of modified electrode occurs at lower potentials than that of an unmodified carbon paste electrode, and both an enhancement of the anodic peak current and a signal narrower and better defined with the modified electrode were observed. Accordingly, a method for the determination of sulfamethazine was developed using differential pulse voltammetry, at pH 11 and with an accumulation time of 3 min. The oxidation of sulfamethazine exhibited a dynamic range between 30 and 300 mug/mL and detection and quantitation limits of 54 and 61 mug/mL, respectively. The method was applied to the determination of sulfamethazine in a veterinary commercial solution.

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