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Ferrocene
Kinds of Ferrocene Terms modified by Ferrocene Selected AbstractsOrganically Modified Sol-Gel/Chitosan Composite Based Glucose BiosensorELECTROANALYSIS, Issue 7 2003Xu Chen Abstract A new type of organically modified sol-gel/chitosan composite material was developed and used for the construction of glucose biosensor. This material provided good biocompatibility and the stabilizing microenvironment around the enzyme. Ferrocene was immobilized on the surface of glassy carbon electrode as a mediator. The characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The effects of enzyme-loading, buffer pH, applied potential and several interferences on the response of the enzyme electrode were investigated. The simple and low-cost glucose biosensor exhibited high sensitivity and good stability. [source] Electron Transfer Kinetics of Ferrocene at Microcrystalline Boron-Doped Diamond Electrodes: Effect of Solvent and ElectrolyteELECTROANALYSIS, Issue 4 2003Shannon Haymond Abstract Cyclic voltammetric measurements were made using well-characterized microcrystalline boron-doped diamond thin-film electrodes to test the material's responsiveness for ferrocene as a function of scan rate, solvent, and electrolyte composition. Apparent heterogeneous electron transfer rate constants, k°app, of 0.042±0.015, 0.048±0.015, and 0.008±0.002,cm/s were observed in 0.1,M NaClO4/CH3CN, 0.1,M TBAClO4/CH3CN, and 0.1M TBAClO4/CH2Cl2, respectively. These rate constants, obtained using electrodes without any type of pretreatment, are similar to those observed for freshly polished glassy carbon. The results demonstrate that boron-doped diamond is a viable material for the electrochemical analysis of nonaqueous analytes. [source] Ferrocene Conjugates Containing Diarginine and Aspartic Acid: Salt Bridge Interactions in WaterEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29-30 2009Anas Lataifeh Abstract The ferrocene peptide conjugates of diarginine (MeO-Fc-Arg-Arg-NH2) (1) and aspartic acid [Boc-Fca-Asp(OH)-OH] (2) were found to form a stable 1:1 associate in aqueous solution. The molecular recognition was achieved through a combination of multipoint hydrogen bonding (H-bonding) sites and a guanidinium-carboxylate ion pair. The associate stoichiometry was confirmed by using ESI-MS and NMR experiments; the NMR titration curve shows multiple equilibria with stepwise interconversion from 1:2,,,1:1 binding ratios, and the electrochemical behaviour of the ferrocenyl groups (Fc, Fca) confirm the formation of an ion pair. The CD spectra in the peptide region exhibit a characteristic absorption of a more ordered structure, while the ferrocene helical chirality remains intact. The solid-state IR measurements exclude the involvement of the amide backbone in the interaction.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] An Approach to the Synthesis of Silicon Carbide Nanowires by Simple Thermal Evaporation of Ferrocene onto Silicon WafersEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2007Jun-Jie Niu Abstract Scales of silicon carbide nanowires (SiC-NWs) with high quality were synthesized by direct thermal evaporation of ferrocene onto silicon wafers at high temperature. Ferrocene decomposed into iron and carbon, which was subsequently treated with silicon to form SiC-NWs at high temperature. The SiC-NWs possess small diameters of , 20 nm and lengths of several ,ms. Furthermore, the samples show a uniform morphology, crystalline structure, and a very thin oxide layer. The main crystal direction of [111] was confirmed by high-resolution field-emission-transmission electron microscopy (HR-FETEM). The Raman scattering spectra showed two peaks at , 796 (TO) and , 980 cm,1 (LO) with varying intensity ratios at different positions. The band line fluctuation was contributed to the Raman selection rules. With reference to the experimental results, we suggested a tentative growth model according to the vapor,liquid,solid (VLS) mechanism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Electronic Interactions in Ferrocene- and Ruthenocene-Functionalized Tetraazamacrcocyclic Ligand Complexes of FeII/III, CoII, NiII, CuII and ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2005Peter Comba Abstract The syntheses of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N, -bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1,-diformylferrocene and 1,1,-diformylruthenocene produces the ligands fcmac and rcmac in 81,85% yield. Examination of their CuII, NiII, CoII, ZnII and FeII/III complexes by IR, UV/Vis, EPR and Mössbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [CuII(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance between the two metals is 4.54 Å. Stability constants, determined by potentiometric titration, indicate that the copper(II) complexes are of similar stability as those with unfunctionalized tetraazamacrocyclic ligands (e.g. cyclam = 1,4,8,11-tetraazacyclotetradecane); stability constants of cobalt(II) complexes are about 2 log units smaller, those of nickel(II) and zinc(II) complexes are reduced by more than 10 log units. This selectivity is discussed on the basis of the structural studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis of Triazole-Bridged Unsymmetrical Porphyrin Dyads and Porphyrin,Ferrocene ConjugatesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2010Vijayendra S. Shetti Abstract A simple method has been used to synthesize four porphyrin azides with cores such as N4, N3S, N2SO and N2S2 in 60,90,% yields by treating the corresponding aminoporphyrins with tert -butyl nitrite (tBuONO) and azidotrimethylsilane (TMSN3) in THF/CH3CN under mild reaction conditions. The hitherto unknown aminoporphyrins with heteroatom cores were synthesized from their corresponding nitroporphyrins by standard SnCl2/HCl reduction. The azidoporphyrins were used to synthesize six triazole-bridged unsymmetrical porphyrin dyads containing two different types of porphyrin sub-units as well as five triazole-bridged porphyrin,ferrocene conjugates under CuI -catalyzed "click" reaction conditions. Various CuI -catalyzed reaction conditions were studied and the best yields of triazole-bridged dyads and conjugates were obtained with CuI/DIPEA in THF/CH3CN at room temperature for overnight. The unsymmetrical porphyrin dyads and porphyrin,ferrocene conjugates were characterized by various spectroscopic and electrochemical techniques. In unsymmetrical porphyrin dyads, the NMR, absorption and electrochemical studies indicate a weak interaction between the two porphyrin sub-units. However, preliminary photophysical studies support an efficient singlet-singlet energy transfer from one porphyrin unit to another in five unsymmetrical dyads reported here. In porphyrin,ferrocene conjugates, the fluorescence of porphyrin was quenched significantly due to photo-induced electron transfer from ferrocene to porphyrin. [source] Comparison between the Photophysical Properties of Pyrazolo- and Isoxazolo[60]fullerenes with Dual Donors (Ferrocene, Aniline and Alkoxyphenyl)EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 13 2007Laura Perez Abstract Two series of new pyrazolo- and isoxazolo[60]fullerenes covalently linked to vinylenephenylene bearing ferrocene, dibutylaniline or dodecyloxyphenyl electron-donor groups attached in the periphery have been synthesized. The photophysical properties of these newly synthesized dual-donor,C60 derivatives have been investigated and compared by applying time-resolved fluorescence and nanosecond transient techniques in both polar and nonpolar solvents. Charge separation via the excited singlet state of C60 is more efficient in the pyrazolo-C60 triads than in the isoxazolo-C60 triads. It was found that the pyrazoline ring mediates charge separation as a result of the stronger electron-donating character of the nitrogen atom of the pyrazoline ring compared with the oxygen atom of the isoxazoline ring. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] The First Anionic Thia-Fries Rearrangements at Ferrocene: Ready Access to Trifluoromethylsulfonyl-Substituted Hydroxyferrocenes and an Extremely High Interannular Stereoinduction between Cyclopentadienyl LigandsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 8 2010Georg Werner Abstract Attempts originally directed towards the generation of ferrocyne (1,2-dehydroferrocene, 4) and ferrocenediyne (1,2,1,,2,-tetradehydroferrocene, 5) by triflate elimination from the respective ferrocenyl triflates led to the discovery of the first anionic thia-Fries rearrangements at a five-membered ring. These reactions take place with remarkable efficiency under very mild reaction conditions and yield the respective trifluoromethylsulfonyl-substituted ferrocenols. Most remarkably, the reaction starting from 1,1,-ferrocenediyl ditriflate (9) adopts an extremely high interannular stereoinduction in that exclusively the meso rearrangement product, meso -2,2,-bis(trifluoromethylsulfonyl)-1,1,-ferrocenediol (16), is formed, the corresponding racemic product 17 is not observed. It is shown that the second anionic thia-Fries rearrangement proceeds at a much larger rate than the first one. The stereochemistry and the high rate of this reaction are explained on the basis of electronic as well as steric considerations. The redox behavior of some of the unprecedented ferrocene derivatives has been characterized by cyclovoltammetry. [source] An Efficient Approach to Chiral Ferrocene-Based Secondary Alcohols via Asymmetric Hydrogenation of Ferrocenyl KetonesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2006Wing-Sze Lam Abstract P-Phos-ruthenium-DPEN precatalysts have been found to be efficient for the asymmetric hydrogenation of various ferrocenyl ketones. The use of (R)-xylyl-P-PhosRuCl2(R,R)-DPEN generated chiral ferrocenylethanol in 99.3% e.e. with >99% conversion in a 150-g scale. [source] ChemInform Abstract: Preparation of Polymer-Supported Phosphine from Ferrocene for Palladium-Catalyzed Suzuki,Miyaura Cross-Coupling Reactions.CHEMINFORM, Issue 17 2008Hong Wei Yu Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Synthesis of Novel Planar Chiral Ferrocene and Cyclopentadienyl Manganese Tricarbonyl Derivatives and Their Use as Chiral Ligands in the Palladium-Catalyzed Asymmetric Allylic Alkylation.CHEMINFORM, Issue 44 2003Jae Hoon Lee Abstract For Abstract see ChemInform Abstract in Full Text. [source] Asymmetric Addition of Diethylzinc to Aromatic Aldehydes by Chiral Ferrocene-Based Catalysts.CHEMINFORM, Issue 38 2002Tae-Jeong Kim Abstract For Abstract see ChemInform Abstract in Full Text. [source] Reaction of 1,1,-Divinyl Ferrocene with One-Electron Oxidants: Entry into Functionalised [4]Ferrocenophanes and Observation of an Isotope-Dependent Chemoselectivity EffectCHEMISTRY - A EUROPEAN JOURNAL, Issue 19 2010Renate Abstract 1,1,-Divinyl ferrocene (2) reacts with K3[Fe(CN)6] under basic biphasic conditions to give a [4]ferrocenophane (4) in good yield. Incorporating deuterium labels into the internal positions of the vinyl groups of 2 affects the chemoselectivity of the reaction; thus under identical reaction conditions, [D2]- 2 reacts to provide a diol-functionalised [4]ferrocenophane, [D2]- D/L - 6 in addition to the expected keto-alcohol, [D1]- 4. Variants on this one-electron oxidative cyclisation methodology can be used to give other [4]ferrocenophanes; thus, the reaction of 2 with CuCl2 in MeOH or iPrOH leads to dialkoxy [4]ferrocenophanes 19 and 20, respectively, whereas the reaction of 2 with benzyl carbamate in the presence of tBuOCl gives a bis(carbamate)[4]ferrocenophane, 21. Mechanisms to account for the formation of the products, the stereoselectivity, and the unusual isotope-dependent chemoselectivity in the reaction of 2 and [D2]- 2 with K3[Fe(CN)6] are proposed. [source] Muon Implantation of Metallocenes: FerroceneCHEMISTRY - A EUROPEAN JOURNAL, Issue 8 2007Upali Abstract Muon Spin Relaxation and Avoided Level Crossing (ALC) measurements of ferrocene are reported. The main features observed are five high field resonances in the ALC spectrum at about 3.26, 2.44, 2.04, 1.19 and 1.17,T, for the low-temperature phase at 18,K. The high-temperature phase at 295,K shows that only the last feature shifted down to about 0.49,T and a muon spin relaxation peak at about 0.106,T which approaches zero field when reaching the phase transition temperature of 164,K. A model involving three muoniated radicals, two with muonium addition to the cyclopentadienyl ring and the other to the metal atom, is postulated to rationalise these observations. A theoretical treatment involving spin-orbit coupling is found to be required to understand the Fe,Mu adduct, where an interesting interplay between the ferrocene ring dynamics and the spin-orbit coupling of the unpaired electron is shown to be important. The limiting temperature above which the full effect of spin-orbit interaction is observable in the ,SR spectra of ferrocene was estimated to be 584,K. Correlation time for the ring rotation dynamics of the Fe,Mu radical at this temperature is 3.2,ps. Estimated electron g values and the changes in zero-field splittings for this temperature range are also reported. [source] Supramolecular Photomagnetic Materials: Photoinduced Dimerization of Ferrocene-Based Polychlorotriphenylmethyl RadicalsCHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2004Imma Ratera Abstract New ferrocenyl Schiff-base polychlorotriphenylmethyl radicals have been synthesized and characterized. The imino group of one such radical undergoes an irreversible trans to cis structural isomerization induced by light. Such photoinduced isomerization has been monitored by UV/Vis and ESR spectroscopy and also monitored by HPLC. ESR frozen solution experiments at low temperature revealed that the cis isomer dimerizes, showing a strong antiferromagnetic interaction. Although numerous photochromic supramolecular systems have been described, such a photoinduced self-assembly process represents the first example of a one-way photoswitchable magnetic system in which a conversion between a doublet and a singlet ground state species is promoted by a photoinduced dimerization process driven by the formation of hydrogen bonds. DFT calculations on the minimized structure and on the rotational barriers have been performed to establish the origin of such behavior. The effect of the substituents and the media polarity on the photoisomerization of this imine chromophore have also been studied. It has been observed that the efficiency of the process is markedly dependent on the presence and characteristics of electron-donor and electron-acceptor substituents of the ferrocenyl Schiff-base polychlorotriphenylmethyl radicals as well as on the polarity of the solvent. Han estat sintetitzats i caracteritzats nous radicals policlorotrifenilmetílics connectats a una unitat de ferrocè mitjançant una base de Schiff. El grup imino d,un d,aquests radicals experimenta una isomerització estructural irreversible de trans a cis mitjançant la llum. Aquesta isomerització fotoinduïda ha estat seguida amb les tècniques d, UV/Vis, espectroscòpia de RPE així com també mitjançant cromatografia d, HPLC. L,espectre de RPE d,una solució congelada revel.la que L,isòmer cis dimeritza mostrant una forta interacció antiferromagnètica entre monòmers. Malgrat els nombrosos sistemes supramoleculars fotocròmics que han estat descrits fins ara, aquest procés d,autoassemblatge fotoinduït representa el primer exemple d,interruptor magnètic fotoinduït d,un sol sentit en el qual té lloc una conversió de doblet a singlet de L,espècie en estat fonamental promoguda per un procés d,autoassemblatge mitjançant la formació d,enllaços d,hidrogen. S,han realitzat càlculs de DFT de les estructures minimitzades i de les barreres rotacionals per tal de poder establir L,origen d,aquest comportament. També s,ha estudiat L,efecte dels substituents i de la polaritat del medi en la fotoisomerizació d,aquests cromòfors d,imina. S,ha observat que L,eficiència del procés té una dependència molt marcada amb la presència de substituents electro donadors així com també amb la polaritat del dissolvent. [source] Nonlinear Optical Properties of Ferrocene- and Porphyrin,[60]Fullerene DyadsCHEMPHYSCHEM, Issue 7 2007Evangelia Xenogiannopoulou Dr. Abstract A series of novel [60]fullerene,ferrocene and [60]fullerene,porphyrin dyads, in which a fullerene and an electron donating moiety are attached through a flexible triethylene glycol linker are synthesized and their nonlinear optical (NLO) response studied. Specifically, the third-order susceptibility ,(3) of all fullerene derivatives are measured in toluene solutions by the optical Kerr effect (OKE) technique using 532 nm, 35 ps laser pulses and their second hyperpolarizability , are determined. All fullerene dyads studied exhibit enhancement of their NLO response compared to pristine fullerenes which has been attributed to the formation of a charge separated state. All experimentally measured hyperpolarizability , values are also calculated by the semiempirical methods AM1 and PM3. A good correlation is found between the theoretical and experimental values, suggesting that simple semiempirical methods can be employed for the designing and optimization of the fullerene-containing dyads displaying improved nonlinear responses. [source] Voltammetric Studies of the Interactions Between Ferrocene-Labeled Glutathione and Proteins in Solution or Immobilized onto SurfaceELECTROANALYSIS, Issue 16 2009Yong Peng Abstract Glutathione (GSH) tagged with a ferrocene (Fc) label at its C-terminal was synthesized via coupling ferrocenyl amine to glutathione using o -(benzotriazol-1-yl)- N,N,N,,N, -tetramethyluronium (HBTU)/1-hydroxybenzotrizole (HOBt). The presence of Fc yielded well defined voltammetric signals, rendering the Fc-tagged GSH (GSH-Fc) suitable for electrochemical studies of GSH binding to other biological species. The interaction of GSH-Fc with bovine serum albumin (BSA) was investigated, and a binding ratio of 1.41±0.06 (GSH-Fc/BSA) and an affinity constant Ka of 6.53±2.01×106,M,1 were determined. These results compare well with those measured by fluorescence using untagged GSH, suggesting that the attachment of Fc to GSH does not significantly perturb the GSH structure and binding behavior. By contrasting the binding behavior to several compounds that are known to conjugate to different domains of BSA, the voltammetric study confirmed that GSH-Fc binds at subdomain IIA of BSA with high affinity. The versatility of GSH-Fc for studying GSH binding to surface-confined proteins was also demonstrated with the GSH binding to electroinactive Zn-metallothionein (Zn7 -MT) through hydrogen binding at the region between the Zn7 -MT , and , domains. [source] Real Time Electrochemical Monitoring of DNA/PNA Dissociation by Melting Curve AnalysisELECTROANALYSIS, Issue 14 2009Xiaoteng Luo Abstract An immobilization-free electrochemical method is reported for real-time monitoring of the DNA hybrid dissociation between a ferrocene labeled peptide nucleic acid (PNA) and a fully-complementary or single-base-mismatched DNA. This method takes advantages of electrostatic charge characteristics and interactions among the neutrally charged PNA, the negatively charged DNA and the negatively charged electrode surface made of indium tin oxide (ITO). When a ferrocene labeled PNA (Fc-PNA) sequence is hybridized to a complementary DNA strand, electrostatic repulsion between the negatively charged PNA/DNA hybrid and the negative ITO surface retards the diffusion of the electroactive Fc to the electrode, resulting in a much reduced electrochemical signal. On the other hand, when the Fc-PNA is dissociated from the hybrid at elevated temperatures, the neutrally charged Fc-PNA easily diffuses to the electrode with an enhanced electrochemical signal. Therefore, an electrochemical melting curve of the Fc-PNA/DNA hybrid can be obtained by measuring the Fc signal with the increasing temperature. This strategy allows monitoring of the dissociation of the DNA hybrid in real time, which might lead to a simple detection method for single nucleotide polymorphism (SNP) analysis. [source] Study on Glucose Biofuel Cells Using an Electrochemical Noise DeviceELECTROANALYSIS, Issue 14 2008Yueming Tan Abstract An electrochemical noise (ECN) device was utilized for the first time to study and characterize a glucose/O2 membraneless biofuel cell (BFC) and a monopolar glucose BFC. In the glucose/O2 membraneless BFC, ferrocene (Fc) and glucose oxidase (GOD) were immobilized on a multiwalled carbon nanotubes (MWCNTs)/Au electrode with a gelatin film at the anode; and laccase (Lac) and an electron mediator, 2,2,-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS), were immobilized on a MWCNTs/Au electrode with polypyrrole at the cathode. This BFC was performed in a stirred acetate buffer solution (pH,5.0) containing 40,mmol/L glucose in air, with a maximum power density of 8,,W/cm2, an open-circuit cell voltage of 0.29,V, and a short-circuit current density of 85,,A/cm2, respectively. The cell current at the load of 100,k, retained 78.9% of the initial value after continuous discharging for 15,h in a stirred acetate buffer solution (pH,5.0) containing 40,mmol/L glucose in air. The performance decrease of the BFC resulted mainly from the leakage of the ABTS mediator immobilized at the cathode, as revealed by the two-channel quartz crystal microbalance technique. In addition, a monopolar glucose BFC was performed with the same anode as that in the glucose/O2 membraneless BFC in a stirred phosphate buffer solution (pH,7.0) containing 40,mmol/L glucose, and a carbon cathode in Nafion-membrane-isolated acidic KMnO4, with a maximum power density of 115,,W/cm2, an open-circuit cell voltage of 1.24,V, and a short-circuit current density of 202,,A/cm2, respectively, which are superior to those of the glucose/O2 membraneless BFC. A modification of the anode with MWCNTs for the monopolar glucose BFC increased the maximum power density by a factor of 1.8. The ECN device is highly recommended as a convenient, real-time and sensitive technique for BFC studies. [source] Voltammetric Studies of Parallel Electrode Processes Under Low Ionic Strength Conditions.ELECTROANALYSIS, Issue 7 2006Influence of Convection Abstract It is known that either a very strong enhancement or an almost complete depression of the height of one of two waves can be obtained when two analytes (one appropriately charged and one uncharged) are present in a quiet solution containing no supporting electrolyte. In this paper we examine whether these effects can be extended for solutions with forced convection. Three two-analyte mixtures were examined voltammetrically under conditions of no added supporting electrolyte and added convection. The first mixture (1,1,-ferrocenedimethanol and ferrocenesulfonate anion) changes its total charge from ,1 to +1 after electrooxidation of both components. Under all applied conditions, the introduction of convection caused an increase of both waves without changing the wave height ratio. A similar behavior was observed for the mixture of ferrocene and 1,1,-ferrocenedimethanol. For this system the total charge changes from 0 to +2. A substantial influence of convection on the ratio of two waves was found for the third mixture: ferrocene and ferrocenylmethyltrimethylammonium cation (total charge changes from +1 to +3). For this system the convection strongly depressed the migrational effects. The obtained experimental results were verified with simulations using software MIOTRAS. This software is capable of modeling diffusion, migration, convection and following homogenous reactions. The agreement between experiment and simulations was fairly good. [source] Fourier Transformed Large Amplitude Square-Wave Voltammetry as an Alternative to Impedance Spectroscopy: Evaluation of Resistance, Capacitance and Electrode Kinetic Effects via an Heuristic ApproachELECTROANALYSIS, Issue 15-16 2005Abstract A detailed simulation of Fourier transformed large amplitude square-wave voltammetry is presented in the frequency domain for the process Red,Ox+e,. The simulation takes into account the influence of the electrode kinetics (Butler,Volmer model), uncompensated resistance (Ru) and double layer capacitance (Cdl). Of particular significance is the prediction that the even harmonic responses are only detected in the presence of quasi-reversibility or uncompensated resistance, and also are essentially devoid of charging current. In contrast, the DC and odd harmonic AC components exhibit much larger faradaic currents and also contain charging current. Conveniently, detailed analysis of the simulated DC and AC harmonic components reveals the presence of readily recognised patterns of behaviour with unique levels of sensitivity to electrode kinetics, Ru and Cdl, that facilitate quantitative analysis of these terms. These electrochemical parameters are generally calculated by small amplitude impedance spectroscopy and utilisation of linear analysis of equivalent circuits. Experimental studies on the one electron oxidation of ferrocene in dichloromethane (0.1,M Bu4NPF6) and the one electron reduction of [Fe(CN)6]3, in aqueous 0.5,M KCl electrolyte analysed via heuristic forms of data analysis based on recognition of patterns of behaviour, are presented as examples of a reversible process with significant uncompensated resistance and a quasi-reversible process with minimal ohmic drop, respectively. Results demonstrate the advantages of a more intuitively implemented form of data analysis than presently available with conventional forms of impedance spectroscopy. [source] New Strategy for Dehydrogenase Amperometric Biosensors Using Surfactant to Enhance the Sensitivity of Diaphorase/Ferrocene Modified Carbon Paste Electrodes for Electrocatalytic Oxidation of NADHELECTROANALYSIS, Issue 13 2003César Ramírez-Molina Abstract A carbon paste electrode (CPE) modified with diaphorase (DAP) and ferrocene (FcH) has been developed for determination of NADH at low working potential. The sensitivity and operational stability, towards the detection of the reduced form of the nicotinamide adenine dinucleotide (NADH) in flow injection analysis (FIA), were greatly improved (5 times) upon adding Tween 20 into the electrode matrix. The magnitude of the amperometric signal was dependent on DAP, FcH and surfactant loading, into the modified carbon paste electrode. A rapid and repeatable response was observed to the variation of NADH concentration in the vicinity of the electrode surface. Such advantages of the DAP/FcH/Tween 20 modified carbon paste were successfully used in the construction of L -lactate dehydrogenase modified electrodes. The use of this new approach can be generalized to other dehydrogenases and represents a decisive step for a versatile preparation method of amperometric biosensors. [source] Electron Transfer Kinetics of Ferrocene at Microcrystalline Boron-Doped Diamond Electrodes: Effect of Solvent and ElectrolyteELECTROANALYSIS, Issue 4 2003Shannon Haymond Abstract Cyclic voltammetric measurements were made using well-characterized microcrystalline boron-doped diamond thin-film electrodes to test the material's responsiveness for ferrocene as a function of scan rate, solvent, and electrolyte composition. Apparent heterogeneous electron transfer rate constants, k°app, of 0.042±0.015, 0.048±0.015, and 0.008±0.002,cm/s were observed in 0.1,M NaClO4/CH3CN, 0.1,M TBAClO4/CH3CN, and 0.1M TBAClO4/CH2Cl2, respectively. These rate constants, obtained using electrodes without any type of pretreatment, are similar to those observed for freshly polished glassy carbon. The results demonstrate that boron-doped diamond is a viable material for the electrochemical analysis of nonaqueous analytes. [source] Six-Membered N-Heterocyclic Carbenes with a 1,1,-Ferrocenediyl Backbone: Bulky Ligands with Strong Electron-Donor Capacity and Unusual Non-Innocent CharacterEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 31 2009Ulrich Siemeling Abstract The stable, crystalline N-heterocyclic diaminocarbene fc[N(CH2tBu)-C-N(CH2tBu)] (2d, fc = 1,1,-ferrocenediyl) was prepared by deprotonation of its formamidinium precursor fc[N(CH2tBu)-CH-N(CH2tBu)][BF4] (1d) and used for the preparation of the 16 valence electron complexes [Mo(2d)(CO)4], [RhCl(2d)(cod)] (cod = 1,5-cyclooctadiene) and [RhCl(2d)(CO)2]. 1d, 2d and [RhCl(2d)(cod)] were structurally characterised by single-crystal X-ray diffraction studies. The electrochemical properties of 2d, its 2-adamantyl analogue 2c, its complex [RhCl(2d)(CO)2] and of the precursors 1d and 1,1,-bis(neopentylamino)ferrocene were investigated by electrochemistry. The carbenes are easily oxidised to the corresponding radical cation, whose persistent nature is unprecedented in the chemistry of N-heterocyclic carbenes. The spin density is located at the Fe atom and the carbene C atom according to the results of EPR spectroscopic studies and DFT calculations.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Study of the Effect of the Phosphane Bridging Chain Nature on the Structural and Photophysical Properties of a Series of Gold(I) Ethynylpyridine ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2008Montserrat Ferrer Abstract Alkynyl AuI complexes of the type [Au(C,CC5H4N)(PPh3)] (1) [Au2(C,CC5H4N)2 (diphosphane)] [diphosphane = bis(diphenylphosphanyl)methane (2), bis(diphenylphosphanyl)isopropane] (3), bis(diphenylphosphanyl)acetylene (4), 1,2-bis(diphenylphosphanyl)ethane (5), 1,3-bis(diphenylphosphanyl)propane (6), 1,4-bis(diphenylphosphanyl)butane (7), 1,1,-bis(diphenylphosphanyl)ferrocene (8) and [Au3(C,CC5H4N)3(triphos)] [triphos = 1,1,1-tris(diphenylphosphanylmethyl)ethane] (9) were prepared by reaction of [Au(C,CC5H4N)]n with the suitable phosphane. Determination of the X-ray crystal structures of several compounds bearing different carbon backbones between the phosphorus atoms reveals the influence of the nature of the phosphane spacer on the establishment of intra and/or intermolecular gold,gold interactions. The absorption and emission properties of the complexes were analysed by taking into account the presence or absence of intermetallic interactions. Although UV/Vis spectra show differences for compounds with intramolecular Au,Au contacts, a conclusive trend was not observed in the emission behaviour. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] New Heterodimetallic Platinum(II) Complexes Potentially Useful as Molecular SwitchesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2008Sonia Pérez Abstract Four types of platinum(II) complexes of general formulae [Pt(FcCH=NC6H4OH-2)Cl2(L)] [Fc = (,5 -C5H5)Fe(,5 -C5H4), L = dmso (2) or PhCN (3)], [Pt(FcCH=NC6H4O-2)Cl(dmso)] (4), [Pt{(,5 -C5H3CH=NC6H4O-2)Fe(,5 -C5H5)}(L)] [L = dmso (5) or PPh3 (6)] or [Pt{(,5 -C5H3CH=NC6H4OH-2)Fe(,5 -C5H5)}Cl(L)] [L = dmso (7) or PPh3 (8)] have been prepared. These compounds differ in the mode of binding of the ligand: (N) (in 2 and 3), (N,O), (in 4), [C(sp2, ferrocene),N,O]2, (in 5 and 6) or [C(sp2, ferrocene),N], (in 7 and 8). NMR, UV/Vis and electrochemical studies of 2 and 4,8 reveal that these products can be grouped in three pairs [(2c, 4b), (5, 7) and (6, 8)], and one of the compounds of each pair can be easily converted into its partner by a H+/OH, chemical input. The results obtained revealed that these transformations, that affect the spectroscopic and electrochemical properties, are reversible and robust. A study of the relevancy of the mode of binding of compounds 2 and 4,8 upon their potential utility of the new platinum(II) complexes as molecular switches is reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis, X-ray Crystal Structures and Electrochemistry of (Indenyl)ruthenium Complexes Containing dppf and Heterocyclic Thiolato/Thione LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2008Sin Yee Ng Abstract A number of (indenyl)ruthenium complexes containing dppf [1,1,-bis(diphenylphosphanyl)ferrocene] and heterocyclic thiolato/thione ligands have been synthesized. All the complexes were fully characterized by microanalytical and spectroscopic techniques, together with X-ray diffraction analyses for those containing the benzothiazolato (thiolato) and the thiadiazole (thione) ligands. Cyclic voltammetry (CV) experiments indicated that these complexes can be oxidized in three one-electron processes at positive potentials. Differences in chemical reversibility observed during variable-temperature CV experiments indicated that it was likely that the oxidation processes occurred at two electronically noncommunicating sites within the molecules. One site could be assigned as the oxidation of the Ru ion (two one-electron processes), whilst the second site was assigned as the oxidation of the dppf (one one-electron process). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] An Approach to the Synthesis of Silicon Carbide Nanowires by Simple Thermal Evaporation of Ferrocene onto Silicon WafersEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2007Jun-Jie Niu Abstract Scales of silicon carbide nanowires (SiC-NWs) with high quality were synthesized by direct thermal evaporation of ferrocene onto silicon wafers at high temperature. Ferrocene decomposed into iron and carbon, which was subsequently treated with silicon to form SiC-NWs at high temperature. The SiC-NWs possess small diameters of , 20 nm and lengths of several ,ms. Furthermore, the samples show a uniform morphology, crystalline structure, and a very thin oxide layer. The main crystal direction of [111] was confirmed by high-resolution field-emission-transmission electron microscopy (HR-FETEM). The Raman scattering spectra showed two peaks at , 796 (TO) and , 980 cm,1 (LO) with varying intensity ratios at different positions. The band line fluctuation was contributed to the Raman selection rules. With reference to the experimental results, we suggested a tentative growth model according to the vapor,liquid,solid (VLS) mechanism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis, Coordination and Catalytic Utility of Novel Phosphanyl,ferrocenecarboxylic Ligands Combining Planar and Central ChiralityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2007Martin Lama Abstract The chiral ferrocene derivative (R,Rp)-2-[1-(diphenylphosphanyl)ethyl]ferrocenecarboxylic acid (1) is prepared together with selected derivatives resulting from modification at the phosphane moiety [P -oxide (5) and P -sulfide (4)] and the carboxyl group {amides bearing benzyl (6) and (R)- or (S)-1-phenylethyl substituents [(R)- 7 and (S)- 7] at the amide nitrogen atom}. Acid 1 and amide 6 are studied as ligands in rhodium and palladium complexes. Bridge cleavage of the dimer [{Rh(,-Cl)Cl(,5 -C5Me5)}2] with 1 gives [RhCl2(,5 -C5Me5)(1 -,P)] (9) containing P-monodentate 1, which undergoes smooth conversion to the (phosphanylalkyl)ferrocenecarboxylato complex [RhCl(,5 -C5Me5){Fe(,5 -C5H5)(,5 -C5H3 -1-CH(Me)PPh2 -2-COO-,2O,P}] (10) upon treatment with silica gel or alumina. Yet another O,P -chelate complex,[Rh{Fe(,5 -C5H5)(,5 -C5H3 -1-CH(Me)PPh2 -2-COO-,2O,P}(CO)(PCy3)] (11; Cy = cyclohexyl) is obtained directly by an acid-base reaction between the acetylacetonato complex [Rh(acac)(CO)(PCy3)] and 1. Amide 6 reacts with [{Pd(,-Cl)(,3 -C3H5)}2] to give the expected phosphane complex [PdCl(,3 -C3H5)(6 -,P)] (12), while the replacement of the cyclooctadiene (cod) ligand in [PdCl(Me)(cod)] affords the chelate complex [PdCl(Me)(6 -,2O,P)] (13). All compounds are characterised by spectroscopic methods and the solid-state structures of 5, 9, 11, 13, (R,Sp)-2-[1-(diphenylphosphoryl)ethyl]-1-[N -(R)-(1-phenylethyl)carbamoyl]ferrocene [(R)- 8; phosphane oxide from (R)- 7], and the synthetic precursors (R,Sp)-1-bromo-2-[1-(diphenylphosphanyl)ethyl]ferrocene (2) and (R,Sp)-1-bromo-2-[1-(diphenylthiophosphoryl)ethyl]ferrocene (3) determined by single-crystal X-ray diffraction. The catalytic properties of 1 and the amides are probed in enanatioselective rhodium-catalysed hydrogenation and palladium-catalysed asymmetric allylic alkylation. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Reactivity and X-ray Structural Studies in Ligand Substitution of [Cp/(Ind)Ru(dppf)Cl] , Epimerisation in [Cp/(Ind)Ru(Josiphos)Cl] {Cp = ,5 -C5H5, Ind = ,5 -C7H9, dppf = 1,1,-Bis(diphenylphosphanyl)ferrocene, Josiphos = (R)-(,)-1-[(S)-2-(Diphenylphosphanyl)ferrocenyl]ethyldicyclohexylphosphane}EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2007Sin Yee Ng Abstract Ligand substitution of [(Ind)Ru(PPh3)2Cl] (1) led to the isolation of [(Ind)Ru(PPh3){Ph2P(CH2)2C9H7}Cl] (2), [(Ind)Ru(dppf)Cl] (3) and [(Ind)Ru{(Ph2PCH2)3CMe}]PF6 ([4]PF6), and diastereoisomers [(R)- and (S)-(Ind)Ru(Josiphos)Cl] [(R)- 5 and (S)- 5], where (R)-(S)-Josiphos is the ferrocene-based chiral diphosphane ligand (R)-(,)-1-[(S)-2-(diphenylphosphanyl)ferrocenyl] ethyldicyclohexylphosphane. The Cp analogues of 5, viz. (R)- 6 and (S)- 6, were also obtained from [CpRu(PPh3)2Cl] (1a). Josiphos-dependent epimerisation was observed, with conversion of the (S) isomer to the (R) isomer in both cases. Chloride abstraction of 3 with NaPF6 in CH3CN and NaN3 in EtOH gave [(Ind)Ru(dppf)(CH3CN)]PF6 ([7]PF6) and [(Ind)Ru(dppf)(N3)] (8), respectively. The azido ligand in 8 underwent [3+2] dipolar cycloaddition with dimethyl acetylenedicarboxylate to give a N -bound bis(methoxycarbonyl)-1,2,3-triazolato complex, 9. X-ray crystal structures of the new complexes, except (R)- 5, (S)- 5 and (S)- 6, have been determined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] | ||||||||||||||||||||||||||||