1273-86-5Relevant articles and documents
Synthesis and electronic properties of ferrocene-containing organic dyads
Watanabe, Motonori,Chang, Yuan Jay,Chou, Po-Ting,Staykov, Aleksandar,Shibahara, Masahiko,Sako, Katsuya,Ishihara, Tatsumi,Chow, Tahsin J.
, p. 1548 - 1551 (2015)
Novel ferrocene-oligothiophenylene-cyanoacrylic acid in the form of donor-spacer-acceptor dyads was synthesized. The compound with a single unit of thiophenylene showed the lowest energy transition in neutral state. For radical cations, the lowest energy transition appears red-shifted along with the increased number of thiophenylene units. These results suggested that the electronic structure of radical cations is significantly different from that of neutral molecules.
Synthesis and electrochemical properties of a series of ferrocene-containing alcohols
Davis, Wade L.,Shago, Rebotsamang F.,Langner, Ernie H.G.,Swarts, Jannie C.
, p. 1611 - 1616 (2005)
A series of primary ferrocenylalcohols, Fc-(CH2)m-OH with m = 1-4 and Fc = ferrocenyl, was synthesised by reduction of the appropriate ferrocenylcarboxylic acids, Fc-(CH2)n-COOH (n = 0-3) and the ester methyl 4-ferrocenylbutanoate with LiAlH4, the reduction of the γ-ketoacid ferrocylpropanoic acid, Fc-CO-(CH 2)2-COOH, with AlCl3/LiAlH4, and the reduction of ferrocenylcarboxaldehyde, FcCHO, with NaBH4. The secondary ferrocenyl alcohols CpFe(C5H4-CH(OH)-CH 3) and Fe(C5H4-CH(OH)-CH3) 2 were obtained by NaBH4 reduction of acetyl and diacetyl ferrocene. The different reduction methods are compared. The electrochemistry of the alcohols was studied by cyclic voltammetry in CH3CN/0.1 M N(nBu)4PF6 utilising a platinum working electrode. The ferrocenyl group showed reversible electrochemistry with the formal reduction potential (Eo′ versus Fc/Fc+) of the ferrocenyl group inversely proportional to side chain length. The influence of the side chain length on Eo′ was more pronounced for the acids because the electron-withdrawing properties of the carbonyl group is stronger than that of the alcohol group. Ion pairing was found to play a major role in the electrochemical behaviour of ferrocenylmethanol, Fc-CH 2-OH.
Click-chemistry approach to synthesis of functionalized isatin-ferrocenes and their biological evaluation against the human pathogen Trichomonas vaginalis
Singh, Amandeep,Zhang, David,Tam, Christina C.,Cheng, Luisa W.,Land, Kirkwood M.,Kumar, Vipan
, p. 1 - 4 (2019)
Copper-promoted azide-alkyne cycloadditions were attempted to synthesize a series of variedly functionalized 1H-1,2,3-triazole-linked isatin-ferrocene, ferrocenylmethoxy-isatin and isatin-ferrocenyl-chalcone conjugates. The synthesized scaffolds were assayed for their inhibitory activity against T. vaginalis as well as several common normal human flora bacteria. The observed inhibitory activities against T. vaginalis and undetectable inhibition of microflora bacteria suggest that these compounds may be specific against trichomonad protozoa and could serve as a new scaffold for synthesis of novel compounds against this important human pathogen.
Electrochemical investigation on the polycondensation kinetics of silicon alkoxides by functionalization of the silica network by redox species
Audebert,Sallard,Sadki
, p. 1321 - 1325 (2003)
The sol-gel polycondensation of tetramethoxysilane has been followed for the first time by functionalization of the oligomeric silane species with a redox active ferrocene. Recording the decrease of the average diffusion coefficient of the mobile species brings information on the sol or gel state, as well as an easy insight of the polycondensation kinetics.
Formylation of a metathesis-derived: Ansa [4]-ferrocene: A simple route to anticancer organometallics
Bretner, Maria,Buchowicz, W?odzimierz,Kamiński, Rados?aw,Koszytkowska-Stawińska, Mariola,Mazur, Maria,Mrozowicz, Micha?,Ochal, Zbigniew,Wińska, Patrycja
, p. 11504 - 11511 (2020)
Formylation of ansa[4]-ferrocene, obtained through the ruthenium-catalysed olefin metathesis, yields two separable, planar chiral 1,3-and 1,2-ansa-ferrocene aldehydes. Single-crystal X-ray structure analysis reveals that both regioisomers crystallize with spontaneous resolution of the racemate in the chiral P212121 space group with one molecule in the asymmetric unit. The major 1,3-isomer was further transformed into a conjugate with 1,2,3-triazole and uracil using click chemistry as the key synthetic step. This inorganic-organic hybrid displays anticancer activity (MCF-7, A549, MDA-MB-231 cell lines) with EC50 values comparable to those for cisplatin.
Si(OCH2Fc)4: Synthesis, Electrochemical Behavior, and Twin Polymerization
Schliebe, Christian,Pfaff, Ulrike,Gemming, Thomas,Lochenie, Charles,Weber, Birgit,Lang, Heinrich
, p. 3850 - 3860 (2015)
The preparation and twin polymerization of the twin monomer Si(OCH2Fc)4 [Fc = Fe(η5-C5H4)(η5-C5H5)] (2) by the reaction of FcCH2OH (1) with SiCl4 in the presence of pyridine was explored. The electronic properties of 2 were investigated by cyclic voltammetry, square-wave voltammetry, and UV/Vis/near-IR spectroelectrochemistry, which showed a redox separation caused by electrostatic repulsion. Thermally induced condensation of 2 is characteristic, as evidenced by differential scanning calorimetry (DSC) and thermogravimetry coupled mass spectrometry (TG-MS). Upon heating 2 to 210 °C, twin polymerization occurred and a hybrid material was formed that showed similarities with known systems derived from 2,2′-spirobi[4H-1,3,2-benzodioxasiline] (SBS), such as the nanopatterning of the formed silicon dioxide, which is characteristic for twin polymerization. Electron microscopy of this material revealed the absence of typical microstructuring found for other twin polymers, and hence, the herein presented system can be characterized as a borderline system if compared to known twin monomers such as SBS. The copolymerization of 2 and SBS afforded a hybrid material from which porous carbon or silica materials containing iron oxide nanoparticles could be obtained. The oxidation state of the incorporated particles was examined by M?ssbauer experiments, which confirmed that only FeIII was incorporated within the porous carbon and silica materials, respectively. The preparation of iron oxide containing porous carbon capsules was achieved by applying a mixture of 2 and SBS to silicon dioxide spheres (d = 200 nm). After twin polymerization and carbonization, porous carbon capsules with incorporated iron oxide nanostructures were obtained. The straightforward preparation of iron-rich porous carbon and silica materials by twin polymerization of Si(OCH2Fc)4 [Fc = Fe(η5-C5H4)(η5-C5H5)] and 2,2′-spirobi[4H-1,3,2-benzodioxasiline] is reported; the electrochemical properties of Si(OCH2Fc)4 are discussed.
Synthesis of new ferrocenyl derivatives and their use in the first cyclopropanation of fullerene C60 with ferrocenes
Floris, Barbara,Galloni, Pierluca,Seraglia, Roberta,Tagliatesta, Pietro
, p. 202 - 207 (2003)
New ferrocenyl derivatives (a β-ketoester and a β-diester) were synthesised and linked to fullerene C60, with the aim to elucidate factors involved in intramolecular electronic communication. These are the first examples of fullerene functionalised with ferrocenes via the cyclopropanation reaction. The resulting dyads were characterised.
Electrocatalytic hydrocarbon hydroxylation by ethylbenzene dehydrogenase from Aromatoleum aromaticum
Kalimuthu, Palraj,Heider, Johann,Knack, Daniel,Bernhardt, Paul V.
, p. 3456 - 3463 (2015)
We report the electrocatalytic activity of ethylbenzene dehydrogenase (EBDH) from the β-proteobacterium Aromatoleum aromaticum. EBDH is a complex 155 kDa heterotrimeric molybdenum/iron-sulfur/heme protein which catalyzes the enantioselective hydroxylation of nonactivated ethylbenzene to (S)-1-phenylethanol without molecular oxygen as cosubstrate. Furthermore, it oxidizes a wide range of other alkyl-substituted aromatic and heterocyclic compounds to their secondary alcohols. Hydroxymethylferrocenium (FM) is used as an artificial electron acceptor for EBDH in an electrochemically driven catalytic system. Electrocatalytic activity of EBDH is demonstrated with both its native substrate ethylbenzene and the related substrate p-ethylphenol. The catalytic system has been modeled by electrochemical simulation across a range of sweep rates and concentrations of each substrate, which provides new insights into the kinetics of the EBDH catalytic mechanism.
Synthesis of esters of metallocene alcohols and 4,5-dichloroisothiazol-3-carboxylic and 5-arylisoxazole-3-carboxylic acids
Potkin,Dikusar,Kletskov,Petkevich,Semenova,Kolesnik,Zvereva,Zhukovskaya,Rosentsveig,Levkovskaya,Zolotar
, p. 338 - 343 (2016)
Acylation of alkyl- and 1,1′-dialkylferrocene alcohols and diols as well as (3,4,4-trichlorobut-3-ene-1-ol-1-yl)-4,5-cymantrene with dichloroisothiazole- and 5-arylisoxazole-3-carbonyl chlorides has afforded esters containing 1,2-azoles fragments. Some of the obtained compounds have exhibited potentiating action in the binary mixtures with insecticides.
Physicochemical properties of nitrogen-doped carbon nanotubes from metallocenes and ferrocenyl imidazolium compounds
Labulo, Ayomide H.,Ngidi, Nonjabulo P.D.,Omondi, Bernard,Nyamori, Vincent O.
, p. 66 - 75 (2018)
Shaped carbon nanomaterials (SCNMs) were synthesized via the chemical vapour deposition (CVD) technique by using typical metallocenes (ferrocene, nickelocene, cobaltocene, and ruthenocene), and more interestingly, by use of novel ferrocenyl imidazolium derivatives, containing -Cl (FcImCl), -NO2 (FcImNO2) and -CH3 (FcImCH3) substituents as catalysts. Acetonitrile was applied both as a carbon and nitrogen source at temperatures 800–900 °C. The SCNMs, namely, carbon nanotubes (CNTs), carbon spheres (CS), carbon fibres (CF) and amorphous carbons (ACs) were obtained in varying ratios depending on the catalyst and carbon sources. The ferrocenyl imidazolium catalysts produced nitrogen-doped CNTs (N-CNTs) with bamboo-like structures. The yields of various reactions were temperature-dependent, with the highest amount of N-CNTs obtained at 850 °C. In all samples, the composition was mainly of CS and N-CNTs except for nickelocene at 800 °C that gave CFs as a “minor” product. Ferrocene and nickelocene in acetonitrile produced well-aligned N-CNTs while cobaltocene and ruthenocene gave 'spaghetti-like’ structures. In the case of ferrocenyl imidazolium catalyst, a coiled N-CNTs morphology was produced from FcImCl catalyst. Also, higher percentage of N-CNTs with traces of CS were obtained from the FcImCl and FcImCH3 catalysts in acetonitrile at 850 °C, while higher percentage of CS and AC were obtained for FcImNO2 catalyst. In all the catalysts, the use of acetonitrile promoted nitrogen-doping (samples with more disordered and with smaller outer-diameters). Thus, this study demonstrates that the synthesis of N-CNTs from nitrogen-containing ferrocenyl imidazolium compounds as catalyst sources, provided higher percentage of N-CNTs which can be suitable for various application.
