Evaluation of Ferrocene Derivatives as Burn Rate Modifiers in AP/HTPB-Based Composite Propellants

Some ferrocene derivatives like 2,4-dinitrophenylhydrazine derivative of acetyl ferrocene, 1-pyrrolidinylmethyl ferrocene, di-ter-butyl ferrocene and 1,3-diferrocenyl-l-butene (DFB) have been synthesised and characterised by infrared, nuclear magnetic resonance, ultraviolet, iron content, etc. To study the effect of their incorporation on performance, ammonium perchlorate/hydroxyl-terminated polybutadiene-based composite propellants containing these derivatives have been prepared and studied for burn rates, tensile strength and percentage elongation followed by their static test evaluation. A comparison of the properties of propellant containing solid and liquid ferrocene derivatives has been made with those containing Fe/sub 2/O/sub 3/ and n-butyl ferrocene, respectively. The data clearly indicates that these ferrocene derivatives are better than Fe/sub 2/O/sub 3/ and n-butyl errocene. Also, DFB is the best among these derivatives. Like composite propellants, DFB increases burn rate in fuel-rich propellants also

Redox-active ferrocene-modified Cowpea mosaic virus nanoparticles

A naturally occurring nanoparticle, the plant virus Cowpea mosaic virus, can be decorated with ferrocene derivatives, of various linker lengths with amine and carboxylategroups, on the external surface using a range of conjugation strategies. The multiple, organometallic, redox-active ferrocene moieties on the outer surface of the virus are electrochemically independent with reduction potentials that span a potential window of 0.16 V that are dependent on the site of modification and the nature of the ferrocene derivative. The number of ferrocenes coupled to each virus ranges from about 100 to 240 depending upon the conjugation site and the linker length and these redox active units can provide multielectron reservoirs

Synthesis and biological evaluation of anti-Toxoplasma gondii activity of a novel scaffold of thiazolidinone derivatives

We designed and synthesised novel N-substituted 1,3-thiazolidin-4-one derivatives for the evaluation of their anti-Toxoplasma gondii efficacy. This scaffold was functionalised both at the N1-hydrazine portion with three structurally different moieties and at the lactam nitrogen with substituted benzyl groups selected on the basis of our previous structure-activity relationships studies. Using three different assay methods, the compounds were assessed in vitro to determine both the levels of efficacy against the tachyzoites of T. gondii (IC50 = 5-148 μM), as well as any evidence of cytotoxicity towards human host cells (TD50 = 68 to ≥320 μM). Results revealed that ferrocene-based thiazolidinones can possess potent anti-tachyzoite activity (TI =2-64)

Novel π-Extended Quinazoline-Ferrocene Conjugates: Synthesis, Structure, and Redox Behavior

Novel ferrocene conjugates of tricyclic quinazoline derivatives are prepared by condensation of active C-6 methylene groups of mackinazolinones with ferrocenecarbaldehyde. Following this route the conjugated parent alkaloid as well as derivatives with nitro, amino, and alkanoylamino groups at C-2 were attached at the ferrocene moiety, thereby significantly extending the delocalized π system. In addition, the parent compound was subjected to the reaction with ferrocene-1,1'-dicarbaldehyde, giving rise to the symmetrical and unsymmetrical double condensation products – 1,1'-disubstituted ferrocene derivatives, which bear two alkaloid substituents. Some of the compounds obtained were subjected to X-ray crystallographic analyses. The influence of the substituents at C-2 through the extended conjugated π system on the iron atom is reflected by results of cyclovoltammetric measurements

Electrochemistry of ferrocenylphosphines FcCH₂PR₂ (Fc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄); R=Ph, CH₂OH and CH₂CH₂CN), and some phosphine oxide, phosphine sulfide, phosphonium and metal complex derivatives

Electrochemical studies of the free ferrocenylphosphine ligands FcCH₂PR₂ (Fc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄); R=Ph, CH₂OH and CH₂CH₂CN) and some phosphine oxide, phosphine sulfide, phosphonium and metal derivatives are described. The free ligands exhibit complex voltammetric responses due to participation of the phosphorus lone pair in the redox reactions. Uncomplicated ferrocene-based redox chemistry is observed for PV derivatives and when the ligands are coordinated in complexes cis-PtCl₂[FcCH₂P(CH₂OH)₂], PdCl₂[FcCH₂P(CH₂OH)₂], [Au{FcCH₂P(CH₂OH)₂}₂]Cl, RuCl₂(η⁶-C₁₀H₁₄)[FcCH₂P(CH₂OH)₂] and RuCl₂(η⁶-C₁₀H₁₄)(FcCH₂PPh₂). The reaction pathways of the free ligands after one-electron oxidation have been examined in detail using voltammetry, NMR spectroscopy and electrospray mass spectrometry. Direct evidence for formation of a P---P bonded product is presented

1,1′-Fc(4-C6H4CO2Et)2and its unusual salt derivative withZ′ = 5,catena-[Na+]2[1,1′-Fc(4-C6H4CO2−)2]·0.6H2O [1,1′-Fc = (η5-(C5H4)2Fe]

The neutral diethyl 4,4'-(ferrocene-1,1'-diyl)dibenzoate, Fe[[eta]5-(C5H4)(4-C6H4CO2Et)]2 (I), yields (II) (following base hydrolysis) as the unusual complex salt poly[disodium bis[diethyl 4,4'-(ferrocene-1,1'-diyl)dibenzoate] 0.6-hydrate] or [Na+]2[Fe{[eta]5-(C5H4)-4-C6H4CO_2^-}2]·0.6H2O with Z' = 5. Compound (I) crystallizes in the triclinic system, space group P\bar 1, with two molecules having similar geometry in the asymmetric unit (Z' = 2). The salt complex (II) crystallizes in the orthorhombic system, space group Pbca, with the asymmetric unit comprising poly[decasodium pentakis[diethyl 4,4'-(ferrocene-1,1'-diyl)dibenzoate] trihydrate] or [Na+]10[Fe{[eta]5-(C5H4)-4-C6H4CO_2^-}2]5·3H2O. The five independent 1,1'-Fc[(4-C6H4CO2)-]2 dianions stack in an offset ladder (stepped) arrangement with the ten benzoates mutually oriented cisoid towards and bonded to a central layer comprising the ten Na+ ions and three water molecules [1,1'-Fc = [eta]5-(C5H4)2Fe]. The five dianions differ in the cisoid orientations of their pendant benzoate groups, with four having their -C6H4- groups mutually oriented at interplanar angles from 0.6 (3) to 3.2 (3)° (as [pi]...[pi] stacked C6 rings) and interacting principally with Na+ ions. The fifth dianion is distorted and opens up to an unprecedented -C6H4- interplanar angle of 18.6 (3)° through bending of the two 4-C6H4CO2 groups and with several ionic interactions involving the three water molecules (arranged as one-dimensional zigzag chains in the lattice). Overall packing comprises two-dimensional layers of Na+ cations coordinated mainly by the carboxylate O atoms, and one-dimensional water chains. The non-polar Fc(C6H4)2 groups are arranged perpendicular to the layers and mutually interlock through a series of efficient C-H...[pi] stacking contacts in a herringbone fashion to produce an overall segregation of polar and non-polar entities

Crystal structure of bis-[4-(1H-pyrrol-1-yl)phen-yl] ferrocene-1,1'-di-carboxyl-ate: a potential chemotherapeutic drug.

The title iron(II) complex, [Fe(C16H12NO2)2], crystallizes in the ortho-rhom-bic space group Pbca with the Fe(2+) cation positioned on an inversion center. The cyclo-penta-dienyl (Cp) rings adopt an anti conformation in contrast with other substituted ferrocenes in which the Cp rings appear in a nearly eclipsed conformation. The Cp and the aromatic rings are positioned out of the plane, with a twist angle of 70.20 (12)°, and the C(Cp)-C(CO) bond length is shorter than a typical C-C single bond, which suggests a partial double-bond character and delocalization with the Cp π system. The structure of the complex is compared to other functionalized ferrocenes synthesized in our laboratory

‘User-friendly’ primary phosphines and an arsine: synthesis and characterization of new air-stable ligands incorporating the ferrocenyl group

Reaction of FcCH₂CH₂P(O)(OH)₂ or FcCH₂P(O)(OH)(OEt) [Fc=Fe(η⁵-C₅H₄)(η⁵-C₅H₅)] with excess CH₂N₂ followed by reduction with Me₃SiCl–LiAlH₄ gives the air-stable primary phosphines FcCH₂CH₂PH₂ and the previously reported analogue FcCH₂PH₂ in high yields. Reduction of 1,1′-Fc′[CH₂P(O)(OEt)₂] [Fc′=Fe(η⁵-C₅H₄)₂] and 1,2-Fc″[CH₂P(O)(OEt)₂] [Fc″=Fe(η⁵-C₅H₅)(η⁵-C₅H₃)] similarly gives the new primary phosphines 1,1′-Fc′(CH₂PH₂)₂ and 1,2-Fc″(CH₂PH₂)₂, respectively. The arsine FcCH₂CH₂AsH₂, which is also air-stable, has been prepared by reduction of the arsonic acid FcCH₂CH₂As(O)(OH)₂ using Zn/HCl. An X-ray structure has been carried out on the arsine, which is only the second structure determination of a free primary arsine. The molybdenum carbonyl complex [1,2-Fc″(CH₂PH₂)₂Mo(CO)₄] was prepared by reaction of the phosphine with [Mo(CO)₄(pip)₂] (pip=piperidine), and characterized by a preliminary X-ray structure determination. However, the same reaction of 1,1′-Fc′(CH₂PH₂)₂with [Mo(CO)₄(pip)₂] gave [1,1′-Fc′(CH₂PH₂)₂Mo(CO)₄] and the dimer [1,1′-Fc′(CH₂PH₂)₂Mo(CO)₄]₂, characterized by electrospray mass spectrometry. 1,1′-Fc′[CH₂PH₂Mo(CO)₅]₂ and 1,2-Fc″[CH₂PH₂Mo(CO)₅]₂ were likewise prepared from the phosphines and excess [Mo(CO)₅(THF)]