The synthesis of some 1,1 '-ferrocene dichalcogenato complexes containing chromium, molybdenum and tungsten

Both dinuclear [3] ferrocenophane derivatives of the type Fe(C5H4E)(2)[MLn] [E = S,Se; MLn = Cp* - Cr(NO) (1), Cp* Mo(NO) (2a,2b), CpMo(NO) (3), Cp* W(NO) (4a,4b), Ca2Mo (6b), Cp2W (7a)] and trinuclear 1,1' - ferrocene dichalcogenato complexes Fe(C5H4E)(2)[MLn](2)[MLn = Cp* Cr(NO)(2), E = S(8a), Se(8b)] were synthesized and characterized by their IR, H-1 MMR and EI - MS spectra as well as their elemental analyses.

Pentamethylcyclopentadienyl halfsandwich rhodium complexes containing 1,1 '-ferrocene dichalcogenido chelate ligands

The heterobimetallic complexes Cp * Rh(CN Bu-t)(EC5H4)(2)Fe [E = S(2),Se(3), Te(4)] have been synthesized by the reaction of halfsandwich rhodium complex Cp * Rh(CNtBu) Cl-2 with Fe(C5H4ELi)(2). 2THF. Oxidation of 2,3 by AgBF4 to give ferrocenium - type salts [Cp * Rh(CNtBu) (EC5H4)(2)Fe] (+) [BF4] (-) [E = S(5),Se(6)] also occurs readily. The new complexes have been characterized by MS IR, H-1 and C-13 NMR spectroscopy and elemental analysis.

Electrocatalytic oxidation of ascorbic acid by ferrocene in lipid film cast on a glassy carbon electrode

A ferrocene-dimyristoyl phosphatidylcholine (DMPC) film electrode was prepared by casting the solution of ferrocene and DMPC in chloroform onto a glassy carbon electrode surface. Ferrocene retained in the biological membrane gave a couple of irreversible peaks of cyclic voltammogram. The electrode exhibited good electrocatalytic activity for the oxidation of ascorbic acid (H(2)A) in phosphate buffer (pH 6.64) with an anodic peak potential of +340 mV (vs. Ag/AgCl). The anodic current was directly proportional to the square root of the scan rate below 150 mV s(-1). The influence of the pH value was investigated and it was observed that pH 6.64 was the suitable value to the anodic peak potential and current. The thickness of the film and the interference of uric acid were also studied. The electrode can be used to determine H(2)A in the presence of equimolar uric acid. The catalytic peak current increased linearly with the concentration of H(2)A in the range of 1 X 10(-4)-5 X 10(-3) mol L-1.

A hydrogen peroxide biosensor combined HRP doped polypyrrole with ferrocene modified sol-gel derived composite carbon electrode

A novel amperometric biosensor for the detection of hydrogen peroxide is described. The biosensor was constructed by electrodepositing HRP/PPy membrane on the surface of ferrocenecarboxylic acid mediated sol-gel derived composite carbon electrode. The biosensor gives response to hydrogen peroxide in a few seconds with detection limit of 5x10(-7) mol (.) L-1 (based on signal : noise=3). Linear range is up to 0.2 mmol (.) L-1.

Studies of ferrocene derivative diffusion and heterogeneous kinetics in polymer electrolyte by using microelectrode voltammetry

The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.

An ultramicroelectrode study of ferrocene diffusion and heterogeneous electron transfer rate in polyelectrolyte

Steady-state voltammograms at a microdisk electrode are used to measure the diffusion coefficient (D) and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG.MClO(4). The diffusion coefficient and standard heterogeneous rate constant of ferrocene are both smaller in polymer solvents than in monomeric solvents. The D and k(s) of ferrocene have been estimated in PEG containing different concentrations and cations of supporting electrolytes, and the dependencies of D and k(s) on temperature have been observed. These results show that the D and k(s) of ferrocene increase with increasing temperature in polyelectrolyte, and with increasing cation radius of supporting electrolyte, eg D and k(s) increase in the order Bu(4)NClO(4) > NaClO4 > LiClO4. On the other hand, D and k(s) increase with decreasing concentration of supporting electrolyte. The dependence of the half-wave potential (E(1/2)) on the concentration of the supporting electrolyte is also observed. E(1/2) shifts in the negative direction as the concentration of supporting electrolyte increases. (C) 1997 Elsevier Science Ltd.

A study of the dependence of ferrocene diffusion on chain length in polymer electrolytes

The diffusion rates of ferrocene have been estimated in five kinds of poly(ethylene glycol) solution, containing the electrolyte LiClO4, by using non-steady-state chronoamperometry. The D-app of ferrocene increases with increasing temperature, and the dependency of D-app on temperature obeys the Williams-Landel-Ferry equation. The D-app of ferrocene decreases with increasing polymer chain length. Both the chain length and temperature dependence conform to a simple free volume model. A relation between current and polymer chain length is suggested at room and high temperatures.

Study on ferrocene derivatives diffusion dynamics in polymer electrolyte by solid-state voltammetry

The diffusion rates of seven ferrocene derivatives have been estimated in polyelectrolyte PEG . LiClO4 by using non-steady-state chronoamperometry. The D-app of ferrocene derivatives increases with temperature, and the dependency of D-app on temperature obeys the Arrhenius equation. The D-app of ferrocene derivatives decreases with increasing size of electroactive species. The Delta D-app values of D-T>Tm and D-Tferrocene at T < T-m is larger than that at T > T-m in the polyelectrolyte. On the other hand, the diffusion behaviour of ferrocene derivatives is qualitatively analyzed by using cyclic voltammetry. Copyright (C) 1996 Elsevier Science Ltd

A study of the dependence of ferrocene diffusion on electrolyte concentration and size in a polymer medium using non-steady-state chronoamperometry

This article describes a quantitative study of the diffusion rate of ferrocene(Fc) dissolved in ploy(ethylene glycol)(PEG) medium containing MClO(4)(M = Li+, Na+, Bu(4)N(+), Hx(4)N(+)). The apparent diffusion coefficient D-app and the active concentration c(a) of Fc were simultaneously measured by using non-steady-state chronoamperometry. The D-app and c(a) of Fc have been estimated in PEG containing different concentrations and sizes of supporting electrolyte, and the dependence of D-app on ferrocene concentrations has been observed. The values of D-app decrease with increasing concentrations of Fc, increasing concentrations of LiClO4 or the ratio (O:Li) and also with 4 decreasing cation radius of the electrolyte. The temperature dependencies conform to a simple free volume model. The concentration and size of the counterion dependencies of the diffusion rate are similar to the behavior of their dependencies of ionic conductivity in polyelectrolyte.

STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

AMPEROMETRIC GLUCOSE SENSOR WITH FERROCENE AS AN ELECTRON-TRANSFER MEDIATOR

A glucose oxidase (GOD) electrode with ferrocene (Fc) used as an electron transfer mediator has been described. Using Nafion, Fc was modified on a glassy carbon (GC) electrode surface, and glucose oxidase was then immobilized on the Fc-Nafion film, forming a GOD-Fc-Nafion enzyme electrode. The preparation method was quite simple and rapid. The enzyme electrode showed a reversible reaction of the redox couple (Fc+/Fc), used in a biosensor system, displayed a sensitive catalytic current response (response time was less than 20 s) on variation of the glucose concentration, with a wide linear range up to 16 mM and with good repeatability. The enzyme electrode showed almost no deterioration over the course of three weeks. There was little or no interference from electro-active anions, such as ascorbic acid, to the determination of glucose based on Nafion film and lower oxidizing potentials of the enzyme electrode.

A STUDY OF ION KINETIC ENERGY SPECTROMETRY OF FERROCENE DOUBLY CHARGED IONS IN GAS PHASE

The unimolecular charge separation reactions of the doubly charged ions FeC10H102+, FeC10H theta 2+, FeC10H82+ produced in the ion source by electron impact from ferrocene have been studied using Mass analyzed Ion Kinetic Energy Spectrometry (MIKES) technique. From the values of the kinetic energy releases (T), the intercharge distances (R) of the exploding doubly charged ions in their transition structures have been estimated and some structural informations about the transition states can be obtained. The collision induced reactions of the FeC10H102+ ion with Ar have been studied using MIKES, we postulate a new type of continuing reaction which may be "collisional charge separation induced dissociation".

Structural and biological investigation of ferrocene-substituted 3-methylidene-1,3-dihydro-2H-indol-2-ones

The Knoevenagel condensation of 1,3-dihydro-2H-indol-2-one with ferrocene carboxaldehyde afforded an approximate 2:1 mixture of the geometrical isomers (E)- and (Z)-3-ferrocenylmethylidene-1,3-dihydro-2H-indol-2-one respectively in an overall 67% yield; the air and solution-stable isomers were readily separated by preparative thin layer chromatography and their structures were unequivocally elucidated in solution, by (1)H NMR spectroscopy, and in the solid phase, by X-ray crystallography; both isomers of displayed in vitro toxicity against B16 melanoma and Vero cell lines in the micromolar range and inhibited the kinase VEGFR-2 with IC(50) values of ca. 200 nM.