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Hydrosilylation of aldehydes and ketones catalysed by nickel acetate and tricyclohexylphosphine as the catalytic system was demonstrated using polymethylhydrosiloxane as a cheap reducing reagent. The Royal Society of Chemistry 2013.

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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 preparation, electrochemical, electronic, and cation sensing properties of an indole-ferrocene-indole triad, are presented. A salient feature of this new structural motif is that the redox-active organometallic fragment is linked to the indole rings by unsaturated nitrogen functionalities. Triad 4 behaves as a highly selective dual-redox and chromogenic chemosensor molecule for Hg 2+ cations: the oxidation redox peak is anodically shifted (DeltaE1/2 = 210 mV), and the low energy band of the absorption spectrum is red-shifted (Deltalambda = 120 mm), upon complexation with this metal cation. This change in the absorption spectrum is accompanied by a dramatic colour change from orange to green which allows the potential for “naked eye” detection. 1H NMR as well as DFT calculations have been carried out to get information about the molecular sites which are involved in bonding.

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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 attempted coupling of (ferrocenylmethyl)trimethylammonium iodide (1) with 1,4,7-(triformyl)-1,4,7,10-tetraazacyclododecane (2) in water led to the formation of the expected compound 1-(ferrocenemethyl)-4,7,10-(triformyl)-1,4,7,10-tetraazacyclododecane (3). In addition, hydrolysis of the ferrocenyl precursor 1 led to the formation of two other known compounds, hydroxymethylferrocene (4) and bis(ferrocenylmethyl) ether (5). An X-ray crystal structure determination of 4 revealed the presence of H-bonding between the hydroxyl groups of one molecule of 4 and the oxygen atom of an adjacent molecule resulting in a left-handed helical chain of molecules lying along the b-axis direction. The O?O distances are significantly shorter than those found in previously reported structures of hydroxymethylferrocene derivatives indicative of moderate strength H-bonding interactions. In the structure of 5, the orientation of the ferrocenyl groups are staggered relative to a vector comprising the two carbons of the C-O-C linker. Crown Copyright

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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 series of <3>ferrocenophane(FcP) derivatives have been investigated using 57Fe Moessbauer and 1H NMR spectroscopy.For the 2- and 3-acetyl-FcP in neutral and acidic mrdia, proton resonances were assigned by analogy with the unbridged species, which themselves were analysed using specifically alpha deuteriated compounds. 2-Acetyl-FcP exhibited a strongly shielded methyl group due to out of plane deformation of the carbonyl function.The corresponding carbenium ions were produced from the parent alcohols in CF3CO2 and their NMR spectra discussed. <3>Ferrocenophan-6,8-dione(A) was unprotonated in CF3CO2H, monoprotonated in 80percent H2SO4 to give the symmetrical carbenium ion.The NMR spectrum of the ion is fully discussed.Moessbauer spectra of 2- and 3-acetyl-FcP revealed the latter to have an anomalously low value of both quadrupole splitting (QS) and isomer shift (IS).The QS of frozen solutions of A at pH 13 show little change from those of ferrocene indicating that the carbanionic charge creates a symmetrical electron density about the iron atom by repulsion of the r2g electrons.The carbenium ion generated at the 2 position in <3>FcP showed a higher QS than that in the 3-position due to better overlap with e2g orbitals.The symmetrical carbenium ion derived from dehydro-<3>ferrocenophane showed exalted QS values indicative of iron e2g orbital overlap.The effect of bridging on Moessbauer parameters is also discussed.

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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 prevention of ferrocene leakage from an electrode by physical retention of mediator in a cellulose acetate membrane matrix is reported here for the first time. Five types of cellulose acetate membranes were prepared, containing 1.8, 5.3, 8.5, and 20.0% of ferrocene and a membrane containing 1.8% of ferrocene and 0.05% of Nafion in the matrix. All the membranes tested, including a cellulose acetate membrane without ferrocene, were much more resistant to ascorbate interference (12-69 nA mM-1) in comparison to an uncovered glassy carbon electrode (1152 nA mM-1). With increasing amount of ferrocene in the membrane, a decreasing ability of the membrane to retain mediator was observed. Ferrocene-embedded membranes were successfully applied in the construction of a fructose biosensor by immobilisation of PQQ-dependent fructose dehydrogenase. A biosensor with a membrane containing 20.0% of ferrocene in the matrix exhibited the lowest detection limit (3 muM), the shortest response time (45 s) and the highest sensitivity (232 nA mM-1). However, this biosensor was unstable because of ferrocene leaching and after 9 h of continuous use only 15% of the initial activity was observed. The biosensor with a cellulose acetate membrane containing 1.8% of ferrocene and 0.05% of Nafion had better stability characteristics, and retained almost 40% of the initial response after 8 h of continuous use, with similar sensitivity (226 nA mM-1) and response time (75 s).

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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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Several new ferrocene-functionalised porphyrins and a ruthenocene-functionalised porphyrin have been synthesized and studied using electrochemistry, electronic absorbance and resonance Raman spectroelectrochemical techniques. The porphyrin and ferrocene are observed to have limited effect on each other with the properties of the porphyrin dominating the spectroscopy of these molecules. The Royal Society of Chemistry 1999.

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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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In adults with sickle cell disease (SCD), markers of iron burden are associated with excessive production of the angiogenic protein placenta growth factor (PlGF) and high estimated pulmonary artery pressure. Enforced PlGF expression in mice stimulates production of the potent vasoconstrictor endothelin-1, producing pulmonary hypertension. We now demonstrate heme-bound iron (hemin) induces PlGF mRNA >200-fold in a dose- and time-dependent fashion. In murine and human erythroid cells, expression of erythroid Krueppel-like factor (EKLF) precedes PlGF, and its enforced expression in human erythroid progenitor cells induces PlGFmRNA. Hemin-induced expression of PlGF is abolished in EKLF-deficient murine erythroid cells but rescued by conditional expression of EKLF. Chromatin immunoprecipitation reveals that EKLF binds to the PlGF promoter region. SCD patients show higher level expression of both EKLF and PlGF mRNA in circulating blood cells, and markers of iron over load are associated with high PlGF and early mortality. Finally, PlGF association with iron burden generalizes to other human diseases of iron overload. Our results demonstrate a specific mechanistic pathway induced by excess iron that is linked in humans with SCD and in mice to markers of vasculopathy and pulmonary hypertension.

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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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Atomically thin graphene electrodes enable the modulation of interfacial reactivity by means of underlying substrate effects. Here we show that plasmonic excitation of microscopic arrays composed of 50 nm Au nanoparticles situated underneath a graphene interface results in localized enhancements on the electrochemical readout. We used scanning electrochemical microscopy (SECM) in the feedback and H2O2 collection modes to identify the role of the generated plasmons on the electrochemical response. Using electrochemical imaging, supported by finite-element method simulations, we confirmed that a temperature rise of up to ?30 K was responsible for current enhancements observed for mass transfer- limited reactions. On single-layer graphene (SLG) we observed a shift in the onset of H2O2 generation which we traced back to photothermal induced kinetic changes, raising ko? from 1.1 × 10-8 m/s to 2.2 × 10-7 m/s. Thicker 10-layer graphene electrodes displayed only a small kinetic difference with respect to SLG, suggesting that photothermal processes, in contrast to hot carriers, are the main contributor to the observed changes in interfacial reactivity upon illumination. SECM is demonstrated to be a powerful technique for elucidating thermal contributions to reactive enhancements, and presents a convenient platform for studying sublayer and temperature-dependent phenomena over individual sites on electrodes.

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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 range of potentially tetradentate proligands, H2L, derived from aromatic aldehydes and ketones and aliphatic diamines has been prepared. Their vanadyl(IV) and vanadyl(V) complexes [VO(L)] and [VO(L)]+, and also some adducts [VO(L)?VO(L)]+, have been synthesized. The structures of four selected complexes have been determined and it is shown that these must be a result of both steric and electronic factors that make prediction of conformation and stacking difficult. The adducts [VO(L)?VO(L)]+ have structures that persist in solution in dichloromethane, where they can undergo redox chemistry, but they apparently dissociate into their component complexes in the donor solvent acetonitrile. The Royal Society of Chemistry 1999.

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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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Inclusion behavior of negatively charged host molecules, thiacalix[4]arene-p-tetrasulfonate (TC4AS) and [6]arene-p-hexasulfonate (TC6AS), toward (ferrocenylmethyl)trimethylammonium (FcCH2NMe3+), hydroxymethylferrocene (FcCH2OH), ferrocenecarboxylic acid (FcCOOH), and 1,1?-ferrocenedicarboxylic acid (Fc(COOH)2) was studied in aqueous solutions (pH 7.0) with cyclic voltammetry. Upon increasing the concentration of TC4AS to 4-fold of each guest, the anodic peak current density (jp,a) decreased, suggesting inclusion of the ferrocenyl guests in TC4AS. Also oxidation half-wave potential (E1/2) of FcCH2NMe3+, FcCH2OH, and FcCOOH was shifted to cathodic direction, showing preferential inclusion of the oxidative state. Inclusion of neutral guests such as FcCH2OH and Fc+COO- implies that hydrophobic interaction between TC4AS and the guests is the chief driving force for formation of host-guest assembly. The decrease of E1/2 for each guest was in the order: FcCH2NMe3+ > FcCH2OH > FcCOOH, suggesting that electrostatic interaction controls the preference toward oxidative form of the guest. Dicarboxylic Fc(COOH)2 showed decrease of jp,a but increase of E1/2 upon inclusion, suggesting TC4AS preferred reduced form Fc(COOH)2 to oxidized form Fc+(COO-)2. TC6AS behaved similarly to TC4AS but with larger decrease in of E1/2 and jp,a. The larger shift of E1/2 for inclusion of FcCOOH, the oxidative form of which is also neutral (Fc+COO-), than that attained with TC4AS endorses main role of hydrophobic interaction between TCnAS (n = 4, 6) and ferrocenyl guest molecules. Having the most preferential electrostatic interaction, kinetically stable complex was formed between TC6AS and FcCH2NMe3+.

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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