Ferrocene and ferrocene derivatives
Annotated bibliography of ferrocene and derivatives including synthesis, reaction, bonding, and application
FERROCENE↗
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Preliminary Appraisal of Ferrocene as an Igniting Agent for JP-4 Fuel and Fuming Nitric Acid
A preliminary experimental study was made of the properties of ferrocene as a solute and as a suspension in JP-4 fuel, and of the ignition delays of ferrocene - JP-4 mixture with A.F. specification 14104 white fuming nitric acid (WFNA). The investigation covered concentrations of 4 to 10 percent by weight ferrocene, and a temperature range of -40 to 80 F. The solubility of ferrocene in JP-4 is about 5 percent at room temperature and about 1 percent (extrapolated) at -80 F. The solubility is increased somewhat by increased aromatics content. Undissolved ferrocene particles of 100 mesh and smaller settle rapidly in JP-4. Clear solutions of 4 and 5 percent ferrocene in JP-4 fuels containing 10 and 25 percent by volume aromatics, respectively, do not ignite with WFNA at room temperature. Mixtures containing 10 percent ferrocene (100- mesh and smaller undissolved particles in suspension) ignited with vigorous persistent flames at room temperature, but did not ignite at -38 F. The ignition delays at room temperature, however, were widely varied; the range from 85 milliseconds to over 1 second perhaps reflected differences in degree of sedimentation.
Miller, RIley O.↗
Correlation of Spectral and Electrochemical Properties of a Series of Ferrocene Derivatives
Charge-transfer-to-solvent (CTTS) bands are observed in the UV/VIS spectra of a series of ferrocene derivatives (ferrocene; 1,1’-dimethyl; 1,2,3,4,5-pentamethyl; 1,2,3,4,l’,2’,3’,4’-octamethyl; and decamethyl) by the addition of increasing amounts of CCl4 to ethanol solutions. A linear correlation (slope = 8540 per cm/V) was found between the redox potential and the energy of the CTTS band, consistent with electrochemical and photochemical oxidation by removal of an electron from the same molecular orbital. Inclusion of literature data for ruthenocene and [(η^(5)-C5H5)Fe(CO)]4 results in a line with a slope of 8140 per cm/V, within 1 percent of the wavenumber to electron volt conversion factor. Calculation of association constants (K) shows a slight decrease (1.2 to 0.7 per mole fraction) as the bulkiness of the cyclopentadienyl ring increases, consistent with either a steric or a repulsive electronic effect. The extinction coefficient of the CTTS absorption was constant at approximately 1700 per Mcm .
ultraviolet spectroscopy↗
Experiments with ferrocene
Acetylferrocene preparation by reacting ferrocene with acetic anhydride in phosphoric acid and reducing acetylferrocene to alpha-hydroxyethyl ferrocene by potassium borohydride in methanol
Mcmanus, S. P.↗
Ferrocene Containing Copolymers with Improved Electrostatic Dissipation Properties for Advanced Applications
Electrostatic dissipative polymers are used for a variety of functions. Typical methods utilized to transform electrically insulating polymers into either charge dissipative or conductive materials involve incorporating a conductive filler, conductive polymer, oxidizing the surface using plasma, or incorporating surfactants that act as surface wetting agents. Another approach is to synthesize a block copolymer that is expected to result in better electrical properties with minimal impacts to physical, fire, and thermal properties. One such block that can be added into the main chain of polymers is a diol terminated ferrocene oligomer, which is expected to impart electrostatic dissipative properties into the host polymer while concurrently improving the overall fire properties. Previous work with polyurethanes incorporating a ferrocene oligomer into the main chain resulted in much improved fire retardancy. In dealing with electrostatic dissipative materials the important questions are: how easily does the material charge and how quickly can the charge move to ground. One normally describes the materials conductivity, but conductivity only measures the fastest path for an electron not the slowest path. The slowest path is the one of interest, since it is left on the surface and thus can cause discharges. In order to assess ease of charging and decay times corona charge dissipation measurements can accurately assess these properties by introducing a charge on the surface of the material then measuring the surface voltage and the amount of charge deposited. The charge decay curve then will give an indication of a materials electrostatic dissipation properties. Normally, triboelectric testing can be performed, but results vary. Corona charge dissipation results are more repeatable.
Smith, T. M.↗
Synthesis of ferrocene-nitrogen-containing polymers with conjugated bonds
Synthesis of ferrocene-nitrogen-containing polymers with conjugated bonds
CONJUGATED SYSTEM↗
A study of solid-propellant vaporization and diffusion processes Final technical report
Vaporization rate and diffusion coefficient determined for organic additives to polyurethane solid propellants - dioctyl adipate and ferrocene
SOLID PROPELLANT↗
Fabrication and evaluation of polymeric early-warning fire-alarm devices
The electrical resistivities were investigated of some polymers known to be enhanced by the presence of certain gases. This was done to make a device capable of providing early warning to fire through its response with the gases produced in the early phases of combustion. Eight polymers were investigated: poly(phenyl acetylene), poly(p-aminophenyl acetylene), poly(p-nitrophenyl acetylene), poly(p-formamidophenyl acetylene), poly(ethynyl ferrocene), poly(ethynyl carborane), poly(ethynyl pyridine), and the polymer made from 1,2,3,6 tetramethyl pyridazine. A total of 40 usable thin-film sandwich devices and a total of 70 usable interdigitated-electrode lock-and-key devices were fabricated. The sandwich devices were used for measurements of contact linearity, polymer conductivity, and polymer dielectric constant. The lock-and-key devices were used to determine the response of the polymers to a spectrum of gases that included ammonia, carbon nonoxide, carbon dioxide, sulfur dioxide, ethylene, acrolein, water vapor, and normal laboratory air. Strongest responses were to water vapor, ammonia, and acrolein, and depending on the polymer, weaker responses to carbon dioxide, sulfur dioxide, and carbon monoxide were observed. A quantitative theory of device operation, capable of accounting for observed device leakage current and sensitivity, was developed. A prototype detection/alarm system was designed and built for use in demonstrating sensor performance.
Senturia, S. D.↗
Survey of inorganic polymers
A literature search was carried out in order to identify inorganic, metallo-organic, and hybrid inorganic-organic polymers that could serve as potential matrix resins for advanced composites. The five most promising candidates were critically reviewed and recommendations were made for the achievement of their potential in terms of performance and cost. These generic polymer classes comprise: (1) Poly(arylsil sesquioxanes); (2) Poly(silyl arylene siloxanes); (3) Poly(silarylenes); (4) Poly(silicon-linked ferrocenes); and (5) Poly(organo phosphazenes). No single candidate currently possesses the necessary combination of physicomechanical properties, thermal stability, processability, and favorable economics. The first three classes exhibit the best thermal performance. On the other hand, poly (organo phosphazenes), the most extensively studied polymer class, exhibit the best combination of structure-property control, processability, and favorable economics.
Gerber, A. H.↗
Analysis of redox additive-based overcharge protection for rechargeable lithium batteries
The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection, has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. Digital simulation of the overcharge experiment leads to numerical representation of the potential transients, and estimate of the influence of diffusion coefficient and interelectrode distance on the transient attainment of the steady state during overcharge. The model has been experimentally verified using 1,1-prime-dimethyl ferrocene as a redox additive. The analysis of the experimental results in terms of the theory allows the calculation of the diffusion coefficient and the formal potential of the redox couple. The model and the theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.
Narayanan, S. R.↗
A Controlled Arc Welding and Separation Processes for Carbon Nanotubes
Stage 1 for the Carbon Nanotube Project has been completed. This videograph presents the proposal for Stage 2. The goals of this stage are to: (1) produce CNTs under different conditions such as cooling temperature, voltage, current, cathode and anode sizes; (2) use ferrocene to make longer CNTs; (3) characterize CNTs by spectroscopic methods; (4) develop applications of CNTs, i.e., batteries, composites, wires, etc.; and (5) complete the patent application.
Benavides, Jeannette↗
In General, the Total Voltammetric Current from a Mixture of Redox-Active Substances will Not be the Sum of the Currents that Each Substance would Produce Independently at the Same Concentration as in the Mixture
At the potential range where both decamethylferrocene (dMeFc) and ferrocene (Fc) are oxidized with rates controlled by linear diffusion, electrogenerated Fc(+) radicals diffusing outwards from the electrode react quantitatively (K23 C=5.8 x 10(exp 8) with dMeFc diffusing towards the electrode and produce Fc and dMeFc. That reaction replaces dMeFc with Fc, whose diffusion coefficient is higher than that of dMeFc(+), and the total mass-transfer limited current from the mixture is increased by approximately 10%. Analogous observations are made when mass-transfer is controlled by convective-diffusion as in RDE voltammetry. Similar results have been obtained with another, and for all practical purposes randomly selected pair of redox-active substances, [Co(bipy)3](2+) and N - methylphenothiazine (MePTZ); reaction of MePTZ(+) with [Co(bipy)3](2+) replaces the latter with MePTZ, which diffuses faster and the current increases by approximately 20%. The experimental voltammograms have been simulated numerically and the role of (a) the rate constant of the homogeneous reaction; (b) the relative concentrations; and, (c) the diffusion coefficients of all species involved have been studied in detail. Importantly, it was also identified that within any given redox system the dependence of the mass-transfer limited current on the bulk concentrations of the redox-active species is expected to be non-linear. These findings are discussed in terms of their electroanalytical implications.
Leventis, Nicholas↗
Carbon Nanotube Nanoelectrode Array as an Electronic Chip for Ultrasensitive Label-free DNA Detection
A reliable nanoelectrode array based on vertically aligned multi-walled carbon nanotubes (MWNTs) embedded in SiO2 is used for ultrasensitive DNA detection. Characteristic nanoelectrode behavior is observed using low-density MWNT arrays for measuring both bulk and surface immobilized redox species such as K4Fe(CN)6 and ferrocene derivatives. The open-end of MWNTs are found to present similar properties as graphite edge-plane electrodes with wide potential window, flexible chemical functionalities, and good biocompatibility. BRCA1 related oligonucleotide probes with 18 bp are selectively functionalized at the open ends of the nanotube array and specifically hybridized with oligonucleotide targets incorporated with a polyG tag. The guanine groups are employed as the signal moieties in the electrochemical measurements. R(bpy)(sup 2+, sub 3) mediator is used to further amplify the guanine oxidation signal. The hybridization of sub-attomoles of DNA targets is detected electrochemically by combining the MWNT nanoelectrode array with the R(bpy)(sup 2+, sub 3) amplification mechanism. This technique was employed for direct electrochemical detection of label-free PCR amplicon from a healthy donor through specific hybridization with the BRCA1 probe. The detection limit is estimated to be less than 1000 DNA molecules since abundant guanine bases in the PCR amplicon provides a large signal. This system provides a general platform for rapid molecular diagnostics in applications requiring ultrahigh sensitivity, high-degree of miniaturization, and simple sample preparation, and low-cost operation.
Li, Jun↗
Non-Additive Voltametric Currents From a Mixture of Two, Three and Four Redox-Active Compounds and Electroanalytical Implications
We have published recently the effect of dissimilar diffusion coefficients on the size of the voltammetric waves from a mixture of two redox-active compounds. Similarly, at the potential range where three redox-active species, decamethylferrocene (dMeFc), ferrocene (Fc) and N-methylphenothiazine (MePTZ), are oxidized simultaneously with rates controlled by linear diffusion, electrogenerated radicals diffusing outwards from the electrode react with the original species diffusing towards the electrode from the bulk; thus, Fc(+) reacts with dMeFc producing Fc and dMeFc(+), while MePTZ(+) reacts both with dMeFc producing MePTZ and dMeFc(+), and with Fc producing MePTZ and Fc(+). These reactions replace dMeFc with Fc at the second plateau, and both dMeFc and Fc with MePTZ at the third plateau. Since the diffusion coefficients of the three species are not equal, the mass-transfer limited currents of the second and the third oxidation wave plateaus change by approx. 10%. Numerical simulations of the experimental voltamograms support this mechanism. Similar results were also obtained for a mixture of four redoxactive compounds. The implications of this non-additive nature of currents on: (a) the use of internal voltammetric standards for quantitative analysis of a mixture of redox-active compounds; and, (b) the half wave potentials (E1/2) of the 2nd, 3rd and 4th waves for qualitative analysis, will be discussed.
Dass, Amala↗