12093-10-6Relevant articles and documents
PLASTIC PHASE OF FORMYLFERROCENE STUDIED BY X-RAY DIFFRACTION AND MOSSBAUER SPECTROSCOPY.
Sato,Iwai,Sano,Konno
, p. 634 - 638 (1984)
The structures of both the crystal and the plastic phases of formylferrocene have been determined to be orthorhombic by single-crystal X-ray diffraction. The structural change proposes a mechanism of the transition that postulates the translational molecular motion along the a-axis. Moessbauer spectra observed in the plastic phase show little fluctuation of the electric field gradient ascribed to the orientational disorder between x, y, and z axes of the molecule.
β-Ferrocenyl-β-amino alcohols: a new class of central chiral ferrocene derivatives
Catasús, Mònica,Bueno, Agustí,Moyano, Albert,Maestro, Miguel A,Mahía, José
, p. 212 - 226 (2002)
An efficient procedure for the enantioselective synthesis of β-ferrocenyl-β-amino alcohols, a new class of central chiral ferrocene derivatives suitable for the elaboration of auxiliaries and ligands for asymmetric synthesis, is described. Key steps of the method are the catalytic asymmetric dihydroxylation of 1-ferrocenyl alkenes and the regio- and stereoselective azide substitution of the hydroxyl group adjacent to the ferrocene moiety. The stereochemistry of the substitution step has been established by X-ray diffraction analysis of a cyclic derivative. The first catalytic enantioselective synthesis of a β-ferrocenyl-β-amino acid derivative is also disclosed.
A DFT-Elucidated comparison of the solution-phase and SAM electrochemical properties of short-chain mercaptoalkylferrocenes: Synthetic and spectroscopic aspects, and the structure of Fc- CH2CH2-S-S-CH2CH2-Fc
Lewtak, Jan P,Landman, Marilé,Fernández, Israel,Swarts, Jannie C
, p. 2584 - 2596 (2016)
Facile synthetic procedures to synthesize a series of difficult-To-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(n5-C5H5)(n5-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group Pi. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 pa a radical, Fc(CH2)nS, with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S- (CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group E = Epa,monomer - Epc,dimer ≤ 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. 1H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-Assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, δE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-Thioether, Fc(CH)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au.
New synthesis of ferrocene monocarboxylic acid and systematic studies on the preparation of related key-intermediates
Neto, Alberto Federman,Miller, Joseph,De Andrade, Vania Faria,Fujimoto, Susana Yumi,De Freitas Afonso, Marcia Maisa,Archanjo, Fernando Costa,Darin, Vitor Andre,Andrade E Silva, Marcio Luis,Borges, Aurea Donizete Lanchote,Del Ponte, Gino
, p. 209 - 216 (2002)
An improved technique for the preparation of ferrocenecarboxaldehyde and two new methods for the synthesis of ferrocenemonocarboxylic acid from the aldehyde or from acetyl ferrocene are described. Using the aldehyde or the monocarboxylic acid as starting materials, some important ferrocene key intermediates were prepared: monochlorocarbonyl ferrocene, alkali metal and ammonium ferrocenoates, ferrocene carboxyaldehyde diethylacetal, ferrocenecarboxamide, et..., as well as a new ferrocene derivative: piperazinium diferrocenoate.
Graham, P. J.,Lindsay, R. S.,Parshall, G. W.,Peterson, M. L.,Whitman, G. M.
, p. 3416 - 3420 (1957)
Connor, J. A.,Lloyd, J. P.
, (1973)
Light-Triggered Metal Coordination Dynamics in Photoswitchable Dithienylethene-Ferrocene System
Adarsh, Nayarassery N.,Karmakar, Manisha,Mondal, Bijan,Pal, Adwitiya,Thakur, Arunabha
, p. 6086 - 6098 (2021)
The C2-symmetric photochromic molecule 3, containing dithienylethene (DTE) and ferrocene units connected by an alkyne bridge, represents a unique probe where a metal (Hg2+) binds with the central DTE moiety. Both photoisomerized states of 3 (open, 3o; closed, 3c) are found to interact with Hg2+ ion by the S atoms of the DTE core; however, the binding constants (from a UV-vis study) and DFT calculations suggest that the open isomer (3o) binds with the metal ion more strongly than that of the closed isomer (3c). Notably, the course of metal binding does not perturb the inherent photoisomerization properties of the DTE core and the photoswitchability persists even in the metal-coordinated form of 3, however, with a comparatively slower rate. The quantum yields for photocyclization (φo→c) and photocycloreversion (φc→o) in the free form are 0.56 and 0.007, respectively, whereas the photocyclization quantum yield in the Hg2+ complexed species is 0.068, 8.2 times lower than the photocyclization quantum yield (φo→c) of free 3o. Thus, the rate of photoisomerization can be modulated by a suitable metal coordination to the DTE core. The dynamics of photoswitchability in the metal-coordinated form of DTE has been explored by experimental means (UV-vis and electrochemical studies) as well as quantum chemical calculations.
Jutz, C.
, (1959)
Synthesis and Anti-Biofilm Activity of New Ferrocene Schiff Bases
G?ver, T.,Sevgi, F.,Taner, B.
, p. 907 - 910 (2020)
Abstract: Four new Schiff bases have been synthesized. The effectiveness of ferrocenesystems in inhibiting formation of Staphylococcusaureus biofilms is tested. One of studied ferrocene Schiff basesefficiently inhibits formation of methicillin-sensitive S
Enantiospecific alkylations of alanine
Alonso, Francisco,Davies, Stephen G.,Elend, Almut S.,Haggitt, Jane L.
, p. 257 - 264 (1998)
Reaction of ferrocenecarbaldehyde 3 with sodium (S)-alaninate followed by pivaloyl chloride generates (2S,4S)-2-ferrocenyl-3-pivaloyl-4-methyl-1,3-oxazolidin-5-one 5 (>98% de). Compound 5 undergoes stereospecific 4-alkylation with complete retention of configuration on treatment sequentially with lithium diisopropylamide and an appropriate alkyl bromide {benzyl bromide, allyl bromide, crotyl [(E)-2-enyl] bromide, α-bromo-o-xylene, cinnamyl bromide, 2-(bromomethyl)naphthalene, 1-(tert-butoxycarbonyl)-3-(bromomethyl)indole and bromoacetonitrile} to generate the corresponding (2S,4R)-2-ferrocenyl-3-pivaloyl-4-alkyl-4-methyl-1,3-oxazolidin-5-ones 7a-h. Hydrolysis of (2S,4R)-7a-h on Amberlyst-15 generates the free (R)-α-methyl-α-amino acids (R)-8a-h.
A simple synthesis of metallocene aldehydes from lithiometallocenes and N,N-dimethylformamide: ferrocene and ruthenocene aldehydes and 1,1'-dialdehydes
Mueller-Westerhoff, Ulrich T.,Yang, Zheng,Ingram, Georg
, p. 163 - 168 (1993)
Lithioferrocene, 1,1'-dilithioferrocene, lithioruthenocene and 1,1'-dilithioruthenocene all react with N,N-dimethylformamide in diethyl ether to produce the respective aldehydes.The lithiation of the two metallocenes can be steered to maximize the formation of only one of the two aldehydes by choosing either n-butyllithium in the presence of tetramethylethylenediamine (TMEDA) or t-butyllithium (tBuLi) as the metallating reagent: ferrocene mono-aldehydes or 1,1'-dialdehydes are formed with good yields (91percent and 85percent respectively, based on ferrocene), lower yields (50percent) of ruthenocene-1,1'-dialdehyde were obtained under the standard conditions, because the 1,3,1'-trialdehyde also formed in significant (19percent) amounts.Monolithiation by nBuLi and the formation of the ruthenocene monoaldehyde (yield, 66percent) are favoured when TMEDA is used in only catalytic amounts; lithiation of ruthenocene by tBuLi selectively leads to monolithioruthenocene and the mono-aldehyde (yield, 91percent).The products are easily purified by column chromatography.The simplicity and the high yield of these reactions make them much more desirable than the previously known multistep procedures.
Broadhead, G. D.,Osgerby, J. M.,Pauson, P. L.
, (1958)
Cis and Trans Isomers of 1-Hydroxyiminoalkylferrocenes and Their Antioxidant Activity
Sun, Xiqing,Zhang, Jian,Jin, Longfei
, p. 170 - 174 (2013)
Condensation reactions of acylferrocene with hydroxylamine hydrochloride afforded a series of acylferrocene oximes, 1-hydroxyiminoalkylferrocenes (3a-d) and each separated into cis and trans isomers which has antioxidant activity towards DPPH. Kinetics parameters (log Z) for the reaction of samples with DPPH were determined. The result indicates that 1-hydroxyiminoalkylferrocenes have antioxidant properties which are related to the stereochemistry of the a-substituent hydroxyimino group. Because of a long conjugated chain, resulting in electron delocalization, the antioxidant activity of (3a-d) is better than BHT and enhanced with the increase of compounds concentration of (3a-d), but reduced as the bulkiness of the a-substituent hydroximino group increased. The antioxidant activity of 1-hydroxyiminoalkylferrocene was much higher than that of the precursors (acylferrocenes). Antioxidant activity of cis-isomers is slightly bigger than that of trans-isomers.
Ferrocenylethenyl-substituted 1,3,4-oxadiazolyl-1,2,4-oxadiazoles: Synthesis, characterization and DNA-binding assays
Mayer, Jo?o C.P.,Sauer, André C.,Iglesias, Bernardo A.,Acunha, Thiago V.,Back, Davi F.,Rodrigues, Oscar E.D.,Dornelles, Luciano
, p. 1 - 11 (2017)
This article describes the synthesis, characterization and DNA-binding assays of a series of oxadiazoles derived from (E)-3-ferrocenylacrylic acid. The compounds were obtained in satisfactory yields and characterized by NMR and high resolution mass spectrometry analysis. Additionally, the X-Ray characterization of compound 8a was investigated. A series of ferrocenylethenyl-substituted 1,3,4-oxadiazolyl-1,2,4-oxadiazoles was prepared and studied by UV-visible and electrochemical techniques. The characteristic signals of the redox-active ferrocene/ferrocenium couple were monitored, which allowed verification of the influence of electron-withdrawing oxadiazole heterocycles and their dependence on the 1,2,4-oxadiazole substituent. Also, DNA-binding experiments were performed by UV-vis and emission titrations with ct-DNA.
Synthesis and characterization of new ferrocene-containing ionic liquids
Gharib, Bhasem,Hirsch, Andreas
, p. 4123 - 4136 (2014)
A series of several new families of ferrocene-containing imidazolium salts were synthesized by etherification of ferrocene methanol, acylation of ferrocene, and amide coupling of ferrocene carboxylic acid. The etherification was achieved by an acid-catalyzed procedure and very good yields of between 86-93-% were obtained. Next to the nature of the linkage itself, the lengths of the alkyl chains linking the ferrocenyl moiety and the imidazolium group and the nature of the counterions were also varied. Interestingly, a γ-effect can be observed for the ether compounds but this effect was only visible in 13C NMR spectroscopy. These new redox-active ionic liquids were fully characterized by FTIR, 1H, 19F, and 13C NMR spectroscopy, and by MS, HRMS and elemental analysis. A novel series of ferrocenated ionic liquids with different spacer species between the ferrocenyl moiety and the imidazolium group have been developed. The spacer units have been established by amide coupling, etherification and acylation. The latter reaction is strongly influenced by the chain length of the acid chloride and a γ-effect is observable for the ether compounds. Copyright
Picolinamide as a Directing Group on Metal Sandwich Compounds: sp2 C-H Bond Activation and sp3 C-H Bond Oxidation
Hazra, Susanta,Deb, Mayukh,Singh, Jatinder,Elias, Anil J.
, p. 1784 - 1794 (2017)
Palladium catalyzed bis-arylations, -alkylations, and -allylations on the Cp ring of iron and cobalt sandwich compounds have been achieved using the bidentate picolinamide directing group. This directing group along with catalytic Pd(OAc)2 was found to be highly efficient for C-H functionalization, giving up to 87% yields. The palladacyclic intermediate for the C-H activation of the Cp ring has been isolated and structurally characterized for the cobalt sandwich compound [η5-C5H5]Co(η4-C4Ph4). Attempted C-H annulation reactions using picolinamide-derived sandwich compounds did not yield the expected annulated products and instead oxidized the Cp- and picolinamide-bound CH2 unit to aldehydes. Detailed studies on this novel and unprecedented oxidation indicated that this happens only with the assistance of the picolinamide directing group. We have also shown that the sp2 C-H functionalization and the sp3 C-H oxidation can be effectively carried out as a one-pot reaction.
Peet, J. H. J.,Rockett, B. W.
, p. C1 - C3 (1975)
Schloegl, K.
, (1957)
Synthesis and third-order optical nonlinearities of ferrocenyl Schiff base
Jia, Jian-Hong,Tao, Xiao-Min,Li, Yu-Jin,Sheng, Wei-Jian,Han, Liang,Gao, Jian-Rong,Zheng, Yu-Fen
, p. 114 - 118 (2011)
Four ferrocenyl Schiff bases were synthesized from ferrocenecarboxaldehyde and aromatic amine. The yields were 46-73%. These compounds have a D-A structure and third-order nonlinear optical (NLO) properties. The third-order nonlinear optical properties of the compounds were measured using femtosecond degenerate four-wave mixing. The third-order NLO susceptibilities of the compounds were 2.21-3.32 × 10-13 esu. The second-order hyperpolarizabilities of the molecules were 2.10-3.15 × 10-31 esu. The response times were 42-63 fs.
Berger, A.,McEwen, W. E.,Kleinberg, J.
, p. 2274 - 2279 (1961)
Selective anion receptor for fluoride detection using ferrocenyl-boronate derivative
Su, Zhi-Ming,Lin, Cai-Xia,Zhou, Yun-Tao,Xie, Li-Li,Yuan, Yao-Feng
, p. 17 - 26 (2015)
The reaction of ferrocenecarboxaldehyde with (2-aminoethoxy)diphenylborane led to the formation of ferrocenyl-substituted boronate receptor 1, which was characterized by IR, MS, HRMS, 11B, 1H and 13C NMR spectra. The signaling process was confirmed by UV-vis, electrochemistry measurements as well as 1H and 19F NMR spectroscopy. The receptor 1 exhibited high selectivity for F- in CH3CN solution over all the other anions in the DPVs (differential pulse voltammetry). 1H NMR titrations indicated that F- ion induced tautomerism of E- and Z-isomer transformations of the receptor 1 and there were three kinds of protons showing obvious highfield shifts for receptor 1 in DMSO-d6. UV-vis titrations demonstrated that the receptor 1 could bind F- ion forming 1:1 stoichiometric complexes and show high selectivity and sensitivity towards F- ion.
Dixneuf, P.,Dabard, R.
, p. 167 - 171 (1972)
Ferrocene-based porous organic polymer derived high-performance electrocatalysts for oxygen reduction
Zhou, Baolong,Liu, Liangzhen,Cai, Pingwei,Zeng, Guang,Li, Xiaoqiang,Wen, Zhenhai,Chen, Long
, p. 22163 - 22169 (2017)
Two nitrogen-rich porous organic polymers (POPs) were prepared via facile and low-cost Schiff base chemistry with ferrocene (Fc) and melamine/melem as building blocks. Carbonization of these POP precursors results in porous carbon nanohybrids with carbon composites containing crystalline Fe3C/Fe. Characterization based on a variety of techniques demonstrates that the porous carbon nanohybrids feature rich-nitrogen doping, good conductivity and high BET surface area with unique porous structure, endowing them with an excellent catalytic activity toward the oxygen reduction reaction (ORR) in alkaline electrolytes. The catalysts obtained by carbonization at 800 °C (N-Fc-800) exhibit favorable activity with a rather high onset potential and half wave potential of 0.96 and 0.82 V, respectively. Furthermore, a rechargeable zinc-air battery was assembled using the N-Fc-800 as the cathode catalyst. Compared with the commercial Pt/C, the N-Fc-800 based battery displays a considerably high power density of 178 mW cm-2 with a smaller charge-discharge voltage gap of 0.94 V, and holds excellent stability with a less activity decay (1.0%) over long charge-discharge cycles (200 cycles).
Features of the oxidation of certain hydroxy derivatives of ferrocene with molecular oxygen in organic solvents
Fomin,Shirokov,Polyakova
, p. 1361 - 1370 (2008)
Features of the oxidation of hydroxymethylferrocene with molecular oxygen in organic solvent in the presence of weak and strong Broensted acids were studied. The resulting data were compared with published data on ferrocene and hydroxyferrocene oxidation, which made it possible to assess the trend in the oxidation mechanism in going from ferrocene π complexes to their hydroxyferrocene and hydroxymethylferrocene analogs. A conclusion was drawn that each of the ferrocenes reacts with oxygen in quite a specific way.
Novel meso-substituted ferrocene-appended porphyrins: Synthesis, characterization, and electrochemical evaluation
Payami, Elmira,Neshad, Saeed,Aghaiepour, Alireza,Teimuri-Mofrad, Reza
, (2021/09/08)
This paper focuses on the synthesis of the novel ferrocene-appended porphyrin architectures and their zinc metal complexes. Tetraferrocenylporphyrins are a class of organometallic compounds where the porphyrin core is functionalized with a ferrocenyl unit at each of the four meso positions. Tetraferrocenylporphyrin derivatives were synthesized via a direct tetramerization reaction between some ferrocene carboxaldehyde derivatives and pyrrole in the presence of BF3·Et2O as an efficient catalyst. Moreover, a metalation reaction between tetraferrocenylporphyrin derivatives and zinc acetate was applied in the synthesis of related zinc complexes. The structures of the new organometallic compounds were confirmed by Fourier transform infrared spectroscopy (FT-IR), 1H NMR, 13C NMR, UV–vis, and CHNS analyses. The redox-active properties of the synthesized compounds were characterized by cyclic voltammetry (CV) analysis.
