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Sixfold substitution reaction of hexachlorocyclotriphosphazene with 4-ferrocenylphenol gave a covalent hexaferrocenyl cluster in which all six ferrocene units were electrochemically equivalent. On the other hand, reaction of hexachlorocyclotriphosphazene with ferrocene methanol produced ferrocene aldehyde in high yield.

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Reference:
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 chemosensor RF1 that combines a ferrocene unit and a rhodamine block via the linkage of a carbohydrazone binding unit was designed and prepared for the highly selective detection of Hg2+ in natural water. This chemosensor displays great brightness and fluorescence enhancement following Hg2+ coordination within the limit of detection for Hg2+ at 1 parts per billion (ppb). The fluorescence intensities are nearly proportional to the amount of Hg2+ at the ppb level. It is capable of distinguishing between the safe and the toxic levels of inorganic mercury in drinking water. Hg2+-binding also arouses the absorption of the rhodamine moiety in RF1 significantly with the chromogenic detection limit for Hg2+ at 50 ppb. The conventional UV-vis spectroscopic method thus has the potential to provide the critical information about the mercury hazard assessment for industrial wastewater discharging. The obvious and characteristic color change of the titration solution from colorless to pink upon the addition of Hg2+ demonstrates that RF1 can be used for “naked-eye” detection of Hg2+ in water. The Hg2+ complexation also causes a significant shift of the redox potential about the ferrocene/ ferrocenium couple. The electrochemical responses provide the possibility to quantitative analysis of Hg2+ at the parts per million (ppm) level. Preliminary investigations in natural water samples including seawater and freshwater indicate that RF1 offers a direct and immediate Hg2+ detection in complex media, pointing out its potential utility in environment monitoring and assessment. The responses of RF1 are Hg2+ specific, and the chemosensor exhibits high selectivity toward Hg2+ over other Group 12 metals, alkali, alkaline earth metals, and most of the divalent first-row transition metals. The RF1-Hg2+ complex is successfully isolated and the Hg2+-binding is reversible. The crystal structure and spectral properties of its congener RF2 that contains one ferrocene group and two rhodamine 6G moieties were also investigated for a comparison.

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Reference:
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 combined effect of counter ion concentration, temperature and sweep rate on the cyclic voltammetric response of multilayer modified electrodes has been studied on the basis of data obtained for tetracyanoquinodimethane and poly(vinyl-ferrocene) polymer film electrodes, as well as for modified Ni electrode.It is established that the counter ion concentration influences to a great extent the cyclic voltammetric response, which is probably due to the swelling of the polymer film.With increasing counter ion concentration a shrinkage of the polymer layer and accordingly, an increase in the concentration of redox sites in the film occurs.Although this may cause an increase in the rate of electron exchange between the neighbouring redox sites, permeability of the film in respect to the solvent and ions decreases.This effect may be the reason for a diffusional behaviour which can be observed on using concentrated supporting electrolytes even at low sweep rates and high temperatures.The apparent activation energy of the electrochemical steps depends on the counter ion concentration and sweep rate.On the basis of the temperature dependence of peak potentials, an estimate can be made for sweep rate at which surface behaviour can be expected.

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Reference:
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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Ferrocenyl and pyridyl methylenepyrans were obtained from a Wittig reaction between a pyran phosphorane and ferrocenyl or pyridyl-aldehydes. The nucleophilic nature of the exocyclic C-C bond allowed the formylation of these compounds by a Vilsmeier type reaction. All the new products were characterized by IR spectroscopy, 1H and 13C NMR spectroscopy, mass spectroscopy and (or) elemental analysis. Electrochemistry of representative compounds 2, 10 and 13 was undertaken. In addition, a crystal structure of the ferrocenylpyranylidene aldehyde 5 was described, and the pyrylium character of this compound was specified.

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Reference:
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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Aims: Release of large amounts of free heme into circulation, overproduction of reactive oxygen species (ROS), and activation of toll-like receptor-4-dependent responses are considered critical for the ability of heme to promote oxidative stress and to initiate proinflammatory responses, posing a serious threat to the body. A deep understanding of the consequences of heme overload on the regulation of cellular and systemic iron homeostasis is, however, still lacking. Results: The effects of heme on iron metabolism were studied in primary macrophages and in mouse models of acute and chronic hemolysis. We demonstrated that hemolysis was associated with a significant depletion of intracellular iron levels and increased expression of the sole iron exporter protein, ferroportin. The pathophysiological relevance of this mechanism was further demonstrated in sickle cell anemia mice, which, despite chronic hemolysis, maintained high ferroportin expression and increased iron export. We identified a redox active iron species and superoxide as regulators for ferroportin induction by heme. Scavenging the ROS production, by use of a pharmacological antioxidant N-acetylcysteine, prevented ferroportin induction and normalized intracellular iron levels in macrophages and in experimentally induced hemolysis in mice. Innovation: Our data propose that scavenging ROS levels may be a novel therapeutic strategy to balance intracellular iron levels and systemic iron influx in conditions associated with heme overload. Conclusion: This study identifies that the pro-oxidant, and not the proinflammatory, actions of heme profoundly impact on iron homeostasis by critically regulating the expression of ferroportin and iron export in hemolytic conditions.

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Reference:
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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X-ray absorption spectroscopy (XAS) was used to study the electrochemical incorporation of perrhenate anion, from a 0.1 M NH4ReO4 solution, into poly(vinylferrocene) (PVFc) and a modified PVFc (a copolymer of 30% t-butyl acetylferrocene and 70% t-butyl divinyl ferrocene). The polymers were deposited on a carbon cloth current collector from a solution of the polymers in CH2Cl2. In situ XAS measurements were done at the Fe K edge on the reduced polymers and at 0.9 V vs. Ag/AgCl. Ex situ XAS was done at the Re L3 edge after oxidation of the polymers at 0.9 V. The oxidized electrodes were washed in water to remove dissolved NH4ReO4 in the electrode pores. XAS was done both on wet-washed electrodes and on electrodes that were dried. XAS showed that at 0.9 V the Fe was oxidized from a ferrocene to a ferrocenium moiety and the Fe-C bond distance increased from 2.05 to 2.08 A. Both the X-ray absorption near-edge spectroscopy and extended X-ray absorption fine structure (EXAFS) results are consistent with having >75% of the ferrocene moieties in the polymer oxidized at 0.9 V. The Fe K-edge EXAFS showed no direct indication of interaction of Fe with ReO4-. At the Re L3 edge the only indication of interaction of ReO4- with the polymers was a slight change in the XANES features.

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Reference:
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 invention relates to bi-functionalised metallocenes of general formula (I) where Me=a transition metal, preferably chosen from Fe, Ru and Os, Y and Z, when identical are selected from ?(CH2)n?O?, (CH2)?O?[(CH2)2?O]P? and ?(CH2)q?CONH?(CH2)r?O?, or Y=?(CH2)S?NH? and Z=?(CH2)t?COO?, n=a whole number from 3 to 6 inclusive, p=a whole number from 1 to 4 inclusive, q=a whole number from 0 to 2 inclusive, r=a whole number from 0 to 2 inclusive, s=a whole number from 2 to 5 inclusive, t=a whole number from 3 to 6 inclusive, R and R?=H atoms or are protective groups used in oligonucleotide and peptide synthesis, where at least one of R or R? is protective group used in oligonucleotide and peptide synthesis and R and R? are as defined below: (i) when Z and Y are selected from (CH2)n?O?, ?(CH2)?O?[(CH2)2?O]p? and ?(CH2)q?CONH?(CH2)r?O?, then R and R? are protective groups used in oligonucleotide synthesis and R is a group which can leave a free OH group after deprotection, preferably a photolabile group such as monomethroxythoxytrityl, dimethoxytrityl, t-butyldimethylsilyl, acetyl or trifluroacetyl, and R? is a phosphorylated group which can react with a free OH, preferably a phosphodiester, phosphoramidite or H-phosphonate and (ii) when Y=?(CH2)n?NH? and Z=?(CH2)t?COO?, then R is a protective group used in the synthesis of peptides and is an amino-protecting group, preferably 9-fluorenyloxycarbonyl, t-butoxycarbonyl or benzyloxycarbonyl and R?=H. The above is applied in marking.

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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 bioorganometallic ferrocene derivatives are synthesized through a Diversity Oriented Synthesis strategy. Easily available ferrocene bisimines have been transformed into open ferrocenyl bis-beta-lactams. These compounds have demonstrated to be versatile synthons used in further transformations into new ferrocene bis-beta-amino acids. Carefully selected substituents submitted to ring closing metathesis (RCM) and Cu-catalyzed oxidative alkyne coupling conditions have also allowed the conversion of open substrates into ferrocenic macrocyclic bis-beta-lactams. The Royal Society of Chemistry 2009.

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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 magnitude of the current steps due to blocking collisions is shown to be proportional to the square of the particle size, the concentration of the redox mediator, and inversely proportional to the size of the indicator electrode. A theoretical model and a simple analytical expression have been developed that allow for estimation of the average value of the current step magnitude in blocking collisions. Thus, it is now possible to directly relate the size of the analyte to the size of the average current step without worrying about the edge effect. It is proposed that by using the developed model and equations one could monitor the state of analyte species in solution, i.e., whether it is aggregated or not.

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Reference:
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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Acylation of alkyl- and 1,1?-dialkylferrocene alcohols and diols as well as (3,4,4-trichlorobut-3-ene-1-ol-1-yl)-4,5-cymantrene with dichloroisothiazole- and 5-arylisoxazole-3-carbonyl chlorides has afforded esters containing 1,2-azoles fragments. Some of the obtained compounds have exhibited potentiating action in the binary mixtures with insecticides.

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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