- PLASTIC PHASE OF FORMYLFERROCENE STUDIED BY X-RAY DIFFRACTION AND MOSSBAUER SPECTROSCOPY.
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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.
- Sato,Iwai,Sano,Konno
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- α-Cyanoarylethene ferrocene based rod-shaped compounds, synthesis, self-assembly and redox-responsive properties
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A series of novel α-cyanoarylethene ferrocene based rod-shaped compounds consisting of a biphenyl rigid core, connected with multi-alkyl chain substituted benzene unit via ether (–OCH2-) or ester (-OOC-) link at one end, and with ferrocene unit through α-cyano arylethene at the other end were prepared via Suzuki coupling and Knoevenagel condensation reactions as key steps. The effects of the length and number of the alkyl chain as well as the linking groups on the self-assembly properties of these compounds in bulk states and in organic solutions were investigated. In bulk sate, only the single tetradecyl chain compound with ester (-OOC-) link can show liquid crystalline property, while in organic solvents, such compounds can self-assemble into gels with interesting morphologies. Cyclic voltammetry (CV) and Ultraviolet-visible (UV–vis) absorption studies demonstrated redox characteristics of the prepared compounds. Most interesting is the PEG (polyethylene glycol) film containing such compound (1–5%) was observed to be redox sensitive. The color of the prepared film could be regulated by the redox stimulation, indicating such PEG film have potential for high density information storage.
- Tao, Yuan,Chang, Qing,Ding, Wei,Sun, Yue-Yu,Ma, Tao,Cheng, Xiao-Hong
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- β-Ferrocenyl-β-amino alcohols: a new class of central chiral ferrocene derivatives
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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.
- Catasús, Mònica,Bueno, Agustí,Moyano, Albert,Maestro, Miguel A,Mahía, José
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- Chromogenic, Fluorescent, and Redox Sensors for Multichannel Imaging and Detection of Hydrogen Peroxide in Living Cell Systems
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Hydrogen peroxide (H2O2) is an important reactive oxygen species (ROS). Maintaining the H2O2 concentration at a normal level is critical to achieve the normal physiological activities of cells, which otherwise might trigger various diseases. Therefore, it is necessary to develop new and practical multisignaling sensors for both visualization of intracellular H2O2 and accurate detection of extracellular H2O2. In this paper, a novel multichannel signaling fluorescence-electrochemistry combined probe 1 (FE-H2O2) is presented for imaging and detection of H2O2 in living cell systems. In our design, the probe FE-H2O2 consists of a H2O2 reaction site and 4-ferrocenyl(vinyl)pyridine unit which affords chromogenic, fluorescent, and electrochemical signals. These structural motifs yield a combined chromogenic, fluorescent, and redox sensor in a single molecule. Probe FE-H2O2 showed a Turn-On fluorescence response to H2O2, which can be used for monitoring intracellular H2O2 in vivo. Furthermore, the electrochemical response of probe FE-H2O2 was decreased after the addition of H2O2, which can be applied for accurate detection of H2O2 released from living cells. When the fluorescence imaging method is combined with electrochemical analysis technology, it is hopeful that the well-designed multimodule probe can serve as a practical tool for understanding the metabolism and homeostasis of H2O2 in a complex biological system.
- Ni, Yue,Liu, Hong,Dai, Di,Mu, Xiqiong,Xu, Jian,Shao, Shijun
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- 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
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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.
- Lewtak, Jan P,Landman, Marilé,Fernández, Israel,Swarts, Jannie C
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- Synthesis, characterization, and electronic properties of novel Fc-DCM conjugated system; Experimental and computational studies
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Novel Fc-DCM conjugated compound, 2-(2-ferrocenylvinyl-6-methyl-4H-pyran-4-ylidine) malononitrile, in the form of donor-spacer-acceptor dyad has been synthesized by Knoevenagel condensation. 1H and 13C NMR, FT-IR, CHN analysis and along with atomic absorption spectroscopy supported the predicted structure of the product. The electrochemical behaviour of synthesized compound and the electronic absorption spectra were studied in a variety of solvents. Extensive calculations with various combinations of functionals were carried out to compute energy gap (Eg) of ferrocene derivative. The combined functional and basis set approach PBE/6-31+G(d,p) was found to be well-behaved in the calculation of energy gap. B3LYP/6-31G(d) method was applied to do TD-DFT calculations due to its good agreement with experimental data for prediction of UV-Vis spectra.
- Teimuri-Mofrad, Reza,Rahimpour, Keshvar,Ghadari, Rahim
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- New synthesis of ferrocene monocarboxylic acid and systematic studies on the preparation of related key-intermediates
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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.
- 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
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- Site-selective cation-π interaction as a way of selective recognition of the caesium cation using sumanene-functionalized ferrocenes
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The first sumanene-ferrocene probes for efficient and selective caesium cation (Cs+) recognition are reported. The working mechanism of the sumanene moiety as the sensing unit was based on the site-selective cation-π interaction in its neutral state. The interactions with Cs+ were characterized by high association constant values together with low limits of detection.
- Kasprzak, Artur,Sakurai, Hidehiro
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- Simultaneous Construction of Planar and Central Chiralities as Well as Unprecedented Axial Chirality on and around a Ferrocene Backbone
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Simultaneous generation of planar, central and axial chiralities on and around a ferrocene backbone via a d-phenylglycinol-induced intramolecular iminium cyclization was disclosed, which is rare and differs from known methods. A series of chiral spiro[cyclopentadienyl-1,2,3,3a-tetrahydropentalenyliron(II)-1,2′-pyrrolidine] derivatives were prepared acording to the new method, and their structures were characterized unambiguously. The axial chirality caused by the ferrocene backbone and the rigid spiral structure was verified by NOESY and variable-temperature NMR experiments and single-crystal XRD analyses. Mechanism for the stereoselective iminium cyclization reaction was suggested, which was influenced by steric hindrance and hydrogen bonding.
- Li, Hongjie,Jia, Peijing,Qian, Naixin,Li, Shasha,Jiao, Peng
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- Light-Triggered Metal Coordination Dynamics in Photoswitchable Dithienylethene-Ferrocene System
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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.
- Adarsh, Nayarassery N.,Karmakar, Manisha,Mondal, Bijan,Pal, Adwitiya,Thakur, Arunabha
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- Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality
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Reaction of [IrCp?Cl2]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp?,RIr?. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc,Sp,RIr. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.
- Arthurs, Ross A.,Ismail, Muhammad,Prior, Christopher C.,Oganesyan, Vasily S.,Horton, Peter N.,Coles, Simon J.,Richards, Christopher J.
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- Nano islet formation of formyl- and carboxyferrocene, -ruthenocene, -osmocene and cobaltocenium on amine-functionalized silicon wafers highlighted by crystallographic, AFM and XPS studies
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Surface-hydroxylated silicon wafers, 8, were reacted with 3-aminopropyltrimethoxysilane, 9, to create wafers with amine-functionalized surfaces, 10. The metallocenylaldehydes FcCHO, 1 (Fc = ferrocenyl = Fe II(C5H5)(C5H4)), RcCHO, 2 (Rc = ruthenocenyl = RuII(C5H5)(C 5H4)), and OcCHO, 3 (Oc = osmocenyl = Os II(C5H5)(C5H4)) as well as the carboxylic acids FcCOOH, 4, RcCOOH, 5, OcCOOH, 6, and Cc +COOH·PF6-, 7 (Cc+ = cationic cobaltocenium = [CoIII(C5H5)(C 5H4)]+), were reacted with 10 to covalently anchor the metallocenes on the wafers either via an imine (-CHN-) or amide (-NHCO-) bond. The aldehydes were anchored more effectively than the carboxylic acids. Binding energies of all important atoms in all seven systems were determined by XPS measurements. Metal binding energies of the amide-bonded metallocenes were consistently larger (up to 0.6 eV) than those of the imine-anchored systems. AFM and SEM measurements showed that the covalently anchored metallocenes aggregate into nano-islets of diameter between 40 and 100 nm depending on the metallocene and type of anchoring bond. Up to seven additional layers of unreacted metallocenylaldehyde or -acid further stacked on top of the main layer of metallocene to form each islet. These additional layers of metallocene of each islet are stabilized by a large network of secondary and/or tertiary bonding forces. The main film surfaces have average thicknesses ranging between 2 and 6 nm, while film roughness, which is mostly associated with the islets, was with one exception (that of the Oc-CONH- surface 14) between 17% and 68% of the film thickness. The crystal structures for OcCHO, 3, and Cc+COOH·PF6-, 7, was determined and the observed tertiary and secondary intermolecular interactions between independent molecules explains the formation of the nano-islets of each metallocene when anchored onto the aminated silicon wafers.
- Trzebiatowska-Gusowska, Monika,Ga?gor, Anna,Coetsee, Elizabeth,Erasmus, Elizabeth,Swart, Hendrik C.,Swarts, Jannie C.
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- Synthesis and Anti-Biofilm Activity of New Ferrocene Schiff Bases
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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
- G?ver, T.,Sevgi, F.,Taner, B.
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- Flash vacuum pyrolysis study of iron cyclopentadienyl complexes and the crystal structure of O-acetyl-N-(1-ferrocenylpropylidene)hydroxylamine
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Under flash vacuum pyrolysis (FVP) conditions the acylferrocene FcCOCMe3 (1e) cracks to provide isobutene, but other acylferrocenes FcCOR (R = H, Me, Et, Me2CH, Ph or PhCH2) (1a-d, f, g) either were recovered unchanged or underwent t
- Barnes, John C.,Bell, William,Glidewell, Christopher,Howie, R. Alan
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- Enantiospecific alkylations of alanine
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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.
- Alonso, Francisco,Davies, Stephen G.,Elend, Almut S.,Haggitt, Jane L.
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- Multifunctional geometrical isomers of ferrocene-benzo[1,2-b:4,5-b′]difuran-2,6-(3H,7H)-dione adducts: second-order nonlinear optical behaviour and charge transport in thin film OFET devices
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Geometrical isomers of a set of new ferrocene-benzo[1,2-b:4,5-b′]difuran-2,6-(3H,7H)-dione dyads were synthesized and their optical, nonlinear optical (NLO) and electrochemical properties were investigated. The compounds were fully characterized by spectroscopic data and single crystal X-ray analysis in few cases. The second-order nonlinear polarizabilities were measured in chloroform using a femtosecond hyper-Rayleigh scattering (HRS) method at 1300 nm. The dyads exhibit structure-dependent NLO properties, which could be rationalized by correlation with electrochemical and theoretical data. The (Z)-6 chromophore recorded higher βHRS values than the corresponding (E)-6 isomer, in the donor-acceptor (D-A) type dyads. Similarly, in D-A-D chromophore 7, the βHRS values of isomers follow the order (Z,Z) > (E,Z) > (E,E), which matches with the trend of the wavelength of their maximum absorption as well as an increasing band gap in that order. Owing to the inbuilt structural features, two of these D-A compounds were also explored as semiconducting materials in vacuum deposited top contact bottom gated thin film organic field-effect transistors (OFETs). Defying steric restrictions of the ferrocene unit, the triad (Z,Z)-7 depicted an unbalanced (μe: 3 × 10?3 cm?2 V?1 s?1 and μh: 7 × 10?5 cm?2 V?1 s?1) charge transport behaviour. Evaluation of the isomers of the type studied in this investigation constitutes one of very few reports, in particular this study reveals for the first time the semiconducting behaviour of thermally stable redox active Fc based semiconductors.
- Singla, Priya,Van Steerteghem, Nick,Kaur, Navdeep,Ashar,Kaur, Paramjit,Clays, Koen,Narayan,Singh, Kamaljit
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- A simple synthesis of metallocene aldehydes from lithiometallocenes and N,N-dimethylformamide: ferrocene and ruthenocene aldehydes and 1,1'-dialdehydes
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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.
- Mueller-Westerhoff, Ulrich T.,Yang, Zheng,Ingram, Georg
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- The reactions of α-phenyl- and α-ferrocenylcarbinols with diiron nonacarbonyl
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Diiron nonacarbonyl oxidized a series of α-phenylcarbinols to their corresponding aldehydes and ketones.In addition, this resagent converted 4-methoxybenzyl alcohol to 4-methoxybenzyl ether, albeit in low yield.Under the same reaction conditions, oxidation was a minor with a group of α-ferrocenylcarbinols as ether synthesis was the major reaction with those substrates which could not dehydrate; however, stereoselective olefin synthesis predominated when elimination was possible.
- Bankston, D.
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- Cis and Trans Isomers of 1-Hydroxyiminoalkylferrocenes and Their Antioxidant Activity
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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.
- Sun, Xiqing,Zhang, Jian,Jin, Longfei
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- A convenient method for synthesis of novel alkylferrocene derivatives with various functional groups: synthesis, characterization and electrochemical investigation
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Abstract: In this research, new ferrocenylmethylesters were synthesized according to esterification reaction. To reach this purpose, direct and indirect esterification methods were used. Indirect method included Cannizzaro reaction of new alkylferrocenecarboxaldehydes result in production of alkylferrocenecarboxylic acids and alkyl(hydroxymethyl)ferrocene derivatives. Finally, a variety of known procedures were used for converting the new alkylferrocenecarboxylic acids to the corresponding esters. The oxidative esterification reaction was accomplished using K2CO3/I2 as oxidant in the direct method. The advantages of this method are one-pot and single-step reaction and remarkably high total yield of this procedure. The chemical structures were confirmed with FT-IR, 1H NMR, 13C NMR and MASS spectroscopy as well as CHN analysis. Electrochemical behavior of synthesized compounds was studied by cyclic voltammetry, and the relationship between the peak currents and the square root of the scan rate showed that the redox process is diffusion-limited. Graphic abstract: [Figure not available: see fulltext.].
- Teimuri-Mofrad, Reza,Aghaiepour, Alireza,Rahimpour, Keshvar
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- Ferrocenylethenyl-substituted 1,3,4-oxadiazolyl-1,2,4-oxadiazoles: Synthesis, characterization and DNA-binding assays
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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.
- Mayer, Jo?o C.P.,Sauer, André C.,Iglesias, Bernardo A.,Acunha, Thiago V.,Back, Davi F.,Rodrigues, Oscar E.D.,Dornelles, Luciano
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- Chiral platinum(II) compounds containing ferrocenyl Schiff bases acting as (N), (N,O)-, [C(sp2,ferrocene),N]- or [C(sp2,ferrocene),N,O]2- ligands
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A study of the reactions of the following ferrocenyl Schiff bases: (S C)-(+)-[FcCH=NCH(R1)CH2OH] {Fc = (η5-C5H5)Fe(η5-C 5H4), R1 = Me (1a) or CHMe2 (1b)} with cis-[PtCl2(dmso)2] under different experimental conditions is reported. This study enabled the isolation and characterisation of the enantiomerically pure platinum(II) complexes trans-(SC)- [Pt{FcCH=NCH(R1)CH2OH}Cl2(dmso)] {R1 = Me (2a) or CHMe2 (2b)} and cis-(SC)-[Pt{FcCH=NCH(R 1)CH2OH}Cl2(dmso)] {R1 = Me (3a) or CHMe2 (3b)} as well as four isomeric forms of (SC)- [Pt{FcCH=N-CH(R1)CH2O}Cl(dmso)] {R1 = Me or CHMe2} (4-7a,b). These isomers differ in the conformation of the imine {anti-(E) (in 4 and 6) or syn-(Z) (in 5 and 7)} or in the relative arrangement of the nitrogen and the dmso group {trans (in 4 and 5) or cis (in 6 and 7)}. Imines 1 behave as a N-donor ligand in 2 and 3 and as a (N,O) - group in 4-7. We also prepared the diastereomers {(S p,SC) and (Rp,SC)} of the platinacycles [Pt{[(η5-C5H3)CH=NCH(R 1)CH2OH]Fe(η5-C5H 5)}Cl(dmso)] {8 and 9; R1 = Me (Sp,S C) (8a) and (Rp,SC) (9a) or R1 = CHMe2 (Sp,SC) (8b) and (Rp,S C) (9b)}, [Pt{[(η5-C5H3)CH= NCH(R1)CH2O]Fe(η5-C5H 5)}(dmso)] {10 and 11; R1 = Me (Sp,S C) (10a) and (Rp,SC) (11a) or R1 = CHMe2 (Sp,SC) (10b) and (Rp,S C) (11b)} and [Pt{[(η5-C5H 3)CH=NCH(R1)CH2OH]Fe(η5-C 5H5)}Cl(PPh3)] {12 and 13; R1 = Me (Sp,SC) (12a) and (Rp,SC) (13a) or R1 = CHMe2 (Sp,SC) (12b) and (R p,SC) (13b)}, containing a [C(sp2,ferrocene),N] - (in 8, 9, 12 and 13) or a [C(sp2,ferrocene),N,O] 2- (in 10 and 11) group. The X-ray crystal structures of 1b·H2O, 3b, 7b·CH2Cl2·1/ 2H2O and 9a are also reported. Our study allows the elucidation of the factors affecting the preferential formation of a given platinum(II) complex. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Lopez, Concepcion,Caubet, Amparo,Perez, Sonia,Solans, Xavier,Font-Bardia, Merce,Molins, Elies
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- Synthesis and characterization of new ferrocene-containing ionic liquids
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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
- Gharib, Bhasem,Hirsch, Andreas
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- Fluorescent and electrochemical detection of Cu (II) ions in aqueous environment by a novel, simple and readily available AIE probe
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We have devised a novel and fluorescent chemodosimeter (ANT-Fe), possessing an anthracene scaffold as a fluorophore and ferrocene as a redox active unit for selective and sensitive detection of Cu2+ ions in aqueous media. Its synthesis was realized by a simple combination of two commercially available compounds, 2-aminoanthracene and ferrocenecarboxaldehyde, in one-step without required column chromatography for the purification process. The probe offers distinct properties such as aggregation induced emission, dual sensing mode of fluorometric “turn-off” and electrochemical signaling with cathodic shift, high selectivity towards Cu2+ ions, fast response time and low detection limit (2.5 ppb) via C[dbnd]N bond hydrolysis. Detection of Cu2+ ions by ANT-Fe adsorbed on a test paper system with the naked eye as a practical application is also successfully reported.
- Gunduz, Simay,Karaku?, Erman,Liv, Lokman,Ozturk, Turan
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- Picolinamide as a Directing Group on Metal Sandwich Compounds: sp2 C-H Bond Activation and sp3 C-H Bond Oxidation
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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.
- Hazra, Susanta,Deb, Mayukh,Singh, Jatinder,Elias, Anil J.
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- Conditions for manifestation of approachment and orientation effect at the oxidation of ferrocenylacetic acid and its methyl ester by molecular oxygen in organic Solvents
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By comparison of reactivity of the ferrocene derivatives differing in the nature of the substituents the conditions were revealed of their participation as Bronstedt and Lewis acidic centers in the process of the metallocomplex molecular oxidation with oxygen in terms of manifestations of the effects of rapproachment and orientation. From this standpoint were analyzed the experimental data obtained in the oxidation of methyl ferrocenylacetate. A probable mechanism of the process is proposed that includes the molecular and radicalchain macro steps.
- Fomin,Shirokov
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- The first colorimetric receptor for the B4O72- anion based on nitro substituted phenanthroimidazole ferrocene derivatives
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Four phenanthroimidazole ferrocene derivatives (2a-2d) were designed, synthesized and characterized by 1H NMR, 13C NMR and high-resolution mass spectroscopy (HRMS). Recognition of 12 anions by 2a-2d was investigated by UV-Vis absorption analysis, showing that 2b and 2d sensed B4O72- selectively among the tested anions with an obvious color change observed. 1H NMR titrations and theoretical calculations demonstrated that 2b binds B4O72- through O?H hydrogen bonding and O?B interactions between the nitro moiety and the B4O72- anion.
- Wu, Pei,Wang, Guo,Zhou, Lu,Lu, Jing,Wang, Jianchun
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- Synthesis and third-order optical nonlinearities of ferrocenyl Schiff base
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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.
- Jia, Jian-Hong,Tao, Xiao-Min,Li, Yu-Jin,Sheng, Wei-Jian,Han, Liang,Gao, Jian-Rong,Zheng, Yu-Fen
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- Conformationally rigid chiral ferrocene derivative: Synthesis, resolution and stereochemical assignment
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A conformationally rigid chiral molecule LB-I with Lewis basic site has been designed and synthesized in racemic form from ferrocene via Lewis acid mediated diastereoselective cyclization of hydroxy lactam. Both isomers were successfully obtained in enantiomerically pure form through classical resolution using dibenzoyl-D-tartaric acid as the chiral resolving agent in acetone. The nature of the diastereomeric salt formed in the resolution process was investigated by single crystal X-ray crystallographic studies. The absolute configuration of (+)-LB-I was unambiguously assigned as (S,Rp) by single crystal analysis of the salt I obtained from precipitate fraction containing (+)-LB-I and dibenzoyl-D-tartaric acid.
- Achari, Kamsali Murali Mohan,Ramanathan, Chinnasamy Ramaraj
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- Ferrocenylmethyl azide
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The preparation of ferrocenylmethyl azide and its use as a synthetic intermediate is discussed. Acid catalyzed decomposition of the azide provides the novel product bis(ferrocenylmethyl)amine.
- Bublitz
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- Selective anion receptor for fluoride detection using ferrocenyl-boronate derivative
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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.
- Su, Zhi-Ming,Lin, Cai-Xia,Zhou, Yun-Tao,Xie, Li-Li,Yuan, Yao-Feng
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- Organometalloidal derivatives of the transition metals XXVII. Chemical and structural investigations on (ferrocenylacyl)germanes
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(Ferrocenylacyl)germanes, (η5-C5H5)Fe(η5-C5H4)COGeR3 (R3 = Me3 (I), Ph3 (II) have been synthesized and their physical and structural properties investigated, both spectroscopically and via single crystal X-ray analysis.Basicity measurements, via H-bonding to phenol, indicate that I and II are less basic than their silicon analogs, a feature corroborated by infrared and structural analysis.Thus, the ν(C=O) frequencies for I and II at 1594 and 1596 cm-1 are approximately 18 cm-1 higher than the corresponding acylsilanes, and the C=O bond lengths of 1.223 Angstroem are shorter than the silicon analogs, 1.231 Angstroem.
- Sharma, Hemant K.,Cervantes-Lee, Francisco,Pannell, Keith H.
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- Ferrocene-based porous organic polymer derived high-performance electrocatalysts for oxygen reduction
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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).
- Zhou, Baolong,Liu, Liangzhen,Cai, Pingwei,Zeng, Guang,Li, Xiaoqiang,Wen, Zhenhai,Chen, Long
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- Features of the oxidation of certain hydroxy derivatives of ferrocene with molecular oxygen in organic solvents
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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.
- Fomin,Shirokov,Polyakova
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- A hexaferrocenyl cluster based on a cyclotriphosphazene core: Synthesis and electrochemistry
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Sixfold substitution reaction of hexachlorocyclotriphosphazene with 4-ferrocenylphenol gave a covalent hexaferrocenyl cluster in which all six ferrocene units were electrochemically equivalent. On the other hand, reaction of hexachlorocyclotriphosphazene with ferrocene methanol produced ferrocene aldehyde in high yield.
- Sengupta, Saumitra
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- Novel meso-substituted ferrocene-appended porphyrins: Synthesis, characterization, and electrochemical evaluation
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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.
- Payami, Elmira,Neshad, Saeed,Aghaiepour, Alireza,Teimuri-Mofrad, Reza
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- Planar binuclear ferrocene derivative as well as synthesis method and application thereof
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The invention discloses a planar binuclear ferrocene derivative as well as a synthesis method and an application thereof. The planar binuclear ferrocene derivative can be used as a positive active material of a flow battery. The design is reasonable, the structure of the synthesized planar binuclear ferrocene derivative active substance has two active centers, double energy density can be provided under the condition of the same concentration, the planar binuclear ferrocene derivative active substance has an ionic structure, and compared with ferrocene, the solubility of the active substance is further improved; the ferrocene derivative is stable in electrochemical performance, and the battery efficiency and the battery capacity of the flow battery can still be kept at a relatively high level after the flow battery runs for a long time; a natural salt cavern is used as an electrolyte storage cavern, has the advantages of being large in capacity, low in cost, safe and environmentally friendly, and is suitable for being applied to large-scale energy storage power stations.
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Paragraph 0011; 0047-0048; 0057-0059; 0068-0070; 0079-0081
(2021/11/27)
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- Ferrocene modified triphenylamine derivative electrochromic composite material and preparation method thereof (by machine translation)
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The invention discloses a ferrocene modified triphenylamine derivative compound electrochromism material and a preparation method thereof,and the preparation method 4 - comprises the following steps: firstly, the preparation method of the ferrocene-containing diphenylamine dimer comprises the, following steps: firstly, carrying out an oxidation-reduction 4,4' - reaction with perchloric acid; copper 4,4' - 4,4' - Vilsmerier . (by machine translation)
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Page/Page column 6; 11; 13; 15
(2020/02/17)
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- Picolinamide Assisted Oxidation of CH2 Groups Bound to Organic and Organometallic Compounds Using Ferrocene as a Catalyst
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Picolinamide group assisted sp3 C-H bond oxidation of methylene groups to the corresponding carbonyl compounds has been achieved by using simple bottle ferrocene as catalyst and Cu(OAc)2 or tert-butyl peroxybenzoate (TBPB) as oxidant under mild conditions. This method is applicable for picolinamide bound organic as well as organometallic compounds with yields in the range of 46-82%. Control experiments and mechanistic studies indicate that a radical mechanism is responsible for these oxidative transformations in which ferrocene acts as a catalyst.
- Dolui, Pritam,Hazra, Susanta,Deb, Mayukh,Elias, Anil J.
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supporting information
p. 2015 - 2021
(2019/05/16)
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- Novel biferrocene-based phosphoramidite ligands: The combination of a rather unexplored chiral backbone and a privileged ligand scaffold
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A small library of novel chiral monodentate phosphoramidite ligands, characterized by a dihydroazepine-biferrocene backbone was prepared. In order to obtain this biferrocene substructure, a mild and efficient homocoupling was developed. This allowed to synthesize the dihydroazepine ligand precursor and the phosphoramidite ligands with good overall yields and high enantiomeric excess. These ligands were successfully tested in a rhodium(I)-catalyzed hydrogenation of activated olefins.
- Kimpe,Janssens,Bert,Wackens,Goeman,Van der Eycken
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supporting information
(2019/10/16)
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- Reduction of N,N-Dimethylcarboxamides to Aldehydes by Sodium Hydride–Iodide Composite
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A new and concise protocol for selective reduction of N,N-dimethylamides into aldehydes was established using sodium hydride (NaH) in the presence of sodium iodide (NaI) under mild reaction conditions. The present protocol with the NaH-NaI composite allows for reduction of not only aromatic and heteroaromatic but also aliphatic N,N-dimethylamides with wide substituent compatibility. Retention of α-chirality in the reduction of α-enantioriched amides was accomplished. Use of sodium deuteride (NaD) offers a new step-economical alternative to prepare deuterated aldehydes with high deuterium incorporation rate. The NaH-NaI composite exhibits unique chemoselectivity for reduction of N,N-dimethylamides over ketones.
- Chan, Guo Hao,Ong, Derek Yiren,Yen, Zhihao,Chiba, Shunsuke
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- Design, synthesis and fungicidal activity studies of 3-ferrocenyl-N-acryloylmorpholine
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Ferrocene and its derivatives have been widely used in many fields and also used to modify and improve the performance. Particularly, their low toxicity also attract much attention in medical and pesticide fields. In order to get fungicides with higher biological activity, ferrocenyl groups were introduced into the skeleton of dimethomorph instead of phenyl groups and a series of 3-ferrocenyl-N-acryloylmorpholine were synthesized. The fungicidal bioassay results indicated that most of compounds showed moderate fungicidal activities against 14 kinds of agricultural pathogenic fungi and some compounds displayed higher fungicidal activities than that of dimethomorph. Intrestlingly, compounds 5(Z) exhibited better fungicidal activity against Sclerotinia sclerotiorum than that of compound 5(E).
- Chen, Peiqi,Liu, Chunjuan,Hu, Jianfeng,Zhang, Hao,Sun, Ranfeng
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p. 113 - 121
(2017/12/12)
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- A ferrocene-containing group of the carbamate compound and its synthesis method
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The invention discloses a carbamate compound containing a ferrocene group and a synthesis method thereof, and belongs to the macromolecule field. The invention also discloses a preparation method of the carbamate compound containing the ferrocene group. The carbamate compound containing the ferrocene group has good chemical property stability and has various catalytic properties; the carbamate compound is used in a lubricating oil additive, and besides, has good oxidation resistance, abrasion resistance and corrosion resistance; and the carbamate compound is used in a fuel additive, and has the advantages of suppressing smoke, supporting combustion and reducing pollution.
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Paragraph 0032; 0037; 0042
(2018/02/04)
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- (Planar-Chiral) Ferrocenylmethanols: From Anionic Homo Phospho-Fries Rearrangements to α-Ferrocenyl Carbenium Ions
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The reaction of FcCH2OH with chlorophosphates gave ferrocenyl phosphates FcCH2OP(O)(OR)2 [Fc = Fe(η5-C5H5)(η4-C5H4)], which readily separate into phosphate anions and ferrocenyl carbo-cations. The latter species undergoes consecutive reactions, for example, electrophilic aromatic substitutions. When nitriles, instead of alcohols, are treated with FcLi or tBuLi and chlorophosphates, chiral-pool based ferrocenylimino phosphoramidates Fc-CR=N-P(O)(OR*)2 are formed, which are promising candidates for anionic homo phospho-Fries rearrangements. Moreover, the sterically demanding chiral chlorophosphate with R* enabled oxidative couplings of the imines to form a diferrocenylazine. Similarly, the reaction of Fc–Li with 9-anthrylnitrile produced a 10-ferrocenyl-substituted product, contrary to a reaction at the C≡N functionality. A planar-chiral ortho-P(S)Ph2-functionalized ferrocenylmethanol also gave carbo-cations under acidic conditions. These species can be sulfurized in a unique way giving thio ethers, whereby the in situ formed 1,2-P(S)Ph2,CH2+ ferrocene cation acts as the sulfur and electron source. However, lowering the substrate concentration prevents sulfur migration, resulting in electrophilic substitution reactions with aromatic solvents. Planar-chiral ferrocenylmethyl thio or anisyl derivatives were applied as ligands in Pd-catalyzed Suzuki–Miyaura C,C cross-couplings for the atroposelective synthesis of hindered biaryls with up to 26 % ee at low catalyst loadings (1 mol-% Pd).
- Korb, Marcus,Mahrholdt, Julia,Lang, Heinrich
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supporting information
p. 4028 - 4048
(2017/09/20)
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- Selective oxidation of alcohols using ferrocene-labeled Merrifield resin-supported ionic liquid phase catalysts
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Abstract: A novel ferrocene-labeled Merrifield resin-supported ionic liquid phase catalysts has been synthesized and successfully utilized for the selective oxidation of primary alcohols into corresponding aldehydes. The catalysts were recovered by simple filtration which greatly simplified the purification step and allowed successive reuse for multiple times without significant loss in activity. Graphical Abstract: [Figure not available: see fulltext.]
- Kurane, Rajanikant,Bansode, Prakash,Khanapure, Sharanabasappa,Salunkhe, Rajashri,Rashinkar, Gajanan
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p. 7807 - 7821
(2016/11/25)
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- Acceptorless dehydrogenation of alcohols on a diruthenium(II,II) platform
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The diruthenium(II,II) complex [Ru2(L1)(OAc)3]Cl (1), spanned by a naphthyridine-diimine ligand and bridged by three acetates, has been synthesized. The catalytic efficacy of complex 1 has been evaluated for the acceptorless dehydrogenation (AD) of alcohols and for the dehydrogenative coupling reactions of alcohols with Wittig reagents. The diruthenium(II,II) complex is an excellent catalyst for AD of a diverse range of alcohols, and it is shown to be particularly effective for the conversion of primary alcohols to the corresponding aldehydes without undesired side products such as esters. Triphenylphosphonium ylides in a one-pot reaction with alcohols afforded the corresponding olefins in high yields with excellent E selectivity. The liberated dihydrogen gas was identified and measured to be 1 equiv with respect to alcohol. Deuteration studies with PhCD2OH revealed the absence of isotope scrambling in the product, indicating the involvement of a Ru-monohydride intermediate. Kinetic studies and DFT calculations suggest a low-energy bimetallic β-hydride elimination pathway where rate-limiting intramolecular proton transfer from alcohol to metal-bound hydride constitutes the dehydrogenation step. The general utility of metal-metal bonded compounds for alcohol AD and subsequent coupling reactions is demonstrated here.
- Dutta, Indranil,Sarbajna, Abir,Pandey, Pragati,Rahaman, S. M. Wahidur,Singh, Kuldeep,Bera, Jitendra K.
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p. 1505 - 1513
(2016/06/09)
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- Synthesis of new ferrocenyl 1,3-diazabicyclo[3.1.0]hex-3-ene derivatives
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In this work, several new derivatives of ferrocenyl bicylic aziridine photochromic compounds have been prepared from the premade ketoaziridines and ferrocene carboxaldehyde in the presence of ammonium acetate in absolute ethanol via one-pot, three-component reaction. The structures of the newly synthesized compounds were established on the basis of IR, NMR and UV-Vis spectral studies. The newly synthesized compounds exhibit interesting photochromic behavior in the solid phase and solution state. The photochromic behavior of the prepared compounds has been investigated by UV-Visible spectral data.
- Kiyani, Hamzeh,Fallahnezhad, Saied,Albooyeh, Fereshteh
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p. 168 - 175
(2015/06/23)
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- A ferrocene-pyrene based 'turn-on' chemodosimeter for Cr 3+-application in bioimaging
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Structurally simple, ferrocene-pyrene imine dyad 1 has been developed as a 'turn-on' chemodosimeter for Cr3+. The sensing event is based upon the hydrolysis of the imine functionality. Further, 1, which is also non-cytotoxic (100% cell viability), detects intracellular Cr3+ in the human breast cancer (MCF-7) cells.
- Kaur, Mandeep,Kaur, Paramjit,Dhuna, Vikram,Singh, Sukhdev,Singh, Kamaljit
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p. 5707 - 5712
(2014/04/03)
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- Selective oxidations of activated alcohols in water at room temperature
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Allylic and benzylic alcohols can be selectively oxidized to their corresponding aldehydes or ketones in water containing nanoreactors composed of the designer surfactant TPGS-750-M. The oxidation relies on catalytic amounts of CuBr, bpy, and TEMPO, with N-methyl-imidazole; air is the stoichiometric oxidant. the Partner Organisations 2014.
- Lipshutz,Hageman,Fennewald,Linstadt,Slack,Voigtritter
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supporting information
p. 11378 - 11381
(2014/11/08)
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- A biguanide/Pd-decorated SBA-15 hybrid nanocomposite: Synthesis, characterization and catalytic application
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A stable palladium-decorated SBA-15 nanocomposite was simply fabricated through surface modification of SBA-15 with biguanide and subsequent metal/ligand coordination with Pd2+ from inexpensive commercially available starting materials and using standard laboratory techniques. The structure of this organic inorganic hybrid material was characterized by SEM, TEM, XRD, elemental analyzer, atomic absorption spectroscopy, N2 adsorption-desorption (BET), and FT-IR techniques. The catalytic performance of this novel heterogeneous catalyst was determined for the Suzuki cross-coupling and aerobic oxidation of benzyl alcohols. The composite exhibited an excellent catalytic activity and reuse ability of various recycles in air for the aforementioned organic transformations. TEM images of the recovered catalyst showed retained ordered mesostructure of SBA-15 with no damage in the periodic structure of the silicate framework and a good dispersion of in situ generated palladium nanoparticles within the SBA-15 structure.
- Alizadeh,Khodaei,Kordestania,Beygzadeh
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p. 167 - 174
(2013/05/08)
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- Synthesis and biological evaluation of novel ferrocene-naphthoquinones as antiplasmodial agents
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This work deals with the synthesis and evaluation of new compounds designed by combination of 1,4-naphthoquinone and ferrocene fragments in a 3-ferrocenylmethyl-2-hydroxy-1,4-naphthoquinone arrangement. A practical coupling reaction between 2-hydroxy-1,4-naphthoquinone and ferrocenemethanol derivatives has been developed. This procedure can be carried out "on-water", at moderate temperatures and without auxiliaries or catalysts, with moderate to high yields. The synthesized derivatives have shown significant in vitro antiplasmodial activity against chloroquine-sensitive and resistant Plasmodium falciparum strains and it has been shown that this activity is not related to the inhibition of biomineralization of ferriprotoporphyrin IX. Binding energy calculations and docking of these compounds to cytochrome b in comparison with atovaquone have been performed.
- García-Barrantes, Pedro M.,Lamoureux, Guy V.,Pérez, Alice L.,García-Sánchez, Rory N.,Martínez, Antonio R.,San Feliciano, Arturo
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supporting information
p. 548 - 557
(2013/12/04)
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- Mechanochemical and silica gel-mediated formation of highly electron-poor 1-cyanocarbonylferrocene
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Simple manual grinding of solid cyanomethylferrrocene (1) and silica gel provides a facile one-pot access route to prepare unexpected and highly electron-poor metallocene, 1-cyanocarbonylferrocene (2). Electrochemical measurements supported by computational studies reveal that 2 exhibits the highest FeII/FeIII oxidation potential reported for mono-substituted ferrocenes.
- Nieto, Daniel,Bruna, Sonia,Montero-Campillo, M. Merced,Perles, Josefina,Gonzalez-Vadillo, Ana M.,Mendez, Julia,Mo, Otilia,Cuadrado, Isabel
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p. 9785 - 9787
(2013/10/21)
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- Dehydrogenation of alcohols by bis(phosphinite) benzene based and bis(phosphine) ruthenocene based iridium pincer complexes
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Dehydrogenation of alcohols by three iridium pincer complexes, IrH(Cl)[2,6-(tBu2PO)2C6H 3] (1), {IrH(acetone)[2,6-(tBu2PO) 2C6H3]}{BF4} (2), and IrH(Cl)[{2,5-(tBu2PCH2)2C 5H2}Ru(C5H5)] (3), is reported, in both the presence and the absence of a sacrificial hydrogen acceptor. Dehydrogenation of secondary alcohols proceeds in a catalytic mode with turnover numbers up to 3420 (85% conversion) for acceptorless dehydrogenation of 1-phenylethanol. Primary alcohols are readily decarbonylated even at room temperature to give catalytically inactive 16e Ir-CO adducts. The mechanism of this transformation was studied in detail, especially for EtOH; new intermediates were isolated and characterized.
- Polukeev, Alexey V.,Petrovskii, Pavel V.,Peregudov, Alexander S.,Ezernitskaya, Mariam G.,Koridze, Avthandil A.
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p. 1000 - 1015
(2013/05/08)
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- Tunable ferrocenyl-phosphinite ligands for the ruthenium(II)-catalyzed asymmetric transfer hydrogenation of ketones
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We report here new examples of enantiomerically pure monodendate phosphinite ligands containing both a ferrocene moiety and NH bridging moiety adjacent to the stereocenter, as well as their ruthenium(II) dichloro complexes. The phosphinites based on ferrocenyl moiety possessing stereogenic center have been screened as ligands for ruthenium(II)-catalyzed transfer hydrogenation of aromatic ketones to give corresponding secondary alcohols using iso-PrOH as the hydrogen source in the presence of NaOH. Up to 99% conversion with 97% ee was obtained in the transfer hydrogenation of acetophenone derivatives. Furthermore, the catalytic properties of these catalysts based on ferrocenyl-phosphinite backbone are also discussed briefly. The structures of these ligand and their corresponding complexes have been elucidated by a combination of multinuclear NMR spectroscopy, IR spectroscopy and elemental analysis.
- I?ik, U?ur,Aydemir, Murat,Meri?, Nermin,Durap, Feyyaz,Kayan, Cezmi,Temel, Hamdi,Baysal, Akin
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p. 225 - 233
(2013/10/08)
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- Synthesis, third-order nonlinear optical properties and theoretical analysis of vinylferrocene derivatives
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A series of vinylferrocene derivatives were synthesized from the reaction of ferrocenecarboxaldehyde, alcohol, and triphenylphosphonium bromide in a one-pot, solid-state reaction. Their third-order nonlinear optical (NLO) properties were evaluated in N,N-dimethylformamide at 800 nm using femtosecond degenerate four-wave mixing. The third-order NLO susceptibilities of the compounds were 2.55-3.78 × 10-13 esu. The second-order hyperpolarizabilities of the molecules were 2.42-3.60 × 10-31 esu. The response times were 51-98 fs. The energy of the Highest Occupied Molecular Orbital (HOMO), the Lowest Unoccupied Molecular Orbital (LUMO), the energy gap of the HOMO and LUMO (Egap), natural charge, and molecular orbitals are performed by the Density Function Theory (DFT). The DFT study showed that the third-order NLO properties were increased with the increasing electron-withdrawing ability in accordance with the decreasing Egap and the increasing charge transfer among the donor, π-bridge, and the acceptor. The experiment and theoretical results show that the vinylferrocene derivatives have potential nonlinear optical applications.
- Jia, Jianhong,Cui, Yanhong,Li, Yujin,Sheng, Weijian,Han, Liang,Gao, Jianrong
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p. 273 - 279
(2013/07/19)
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- Aminomethyl-substituted ferrocenes and derivatives: Straightforward synthetic routes, structural characterization, and electrochemical analysis
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A variety of aminomethyl-substituted ferrocenes and the parent compounds (iminomethyl)ferrocenes, azaferrocenophanes, and diferrocenylamines can be selectively synthesized from reductive amination of 1,1′-diformylferrocene or formylferrocene. The optimized one- or two-step reactions have delivered 13 new compounds, isolated in 65-97% yields, which include tertiary (ferrocenylmethyl)amines and azaferrocenophanes by using NaBH(OAc)3 as a mild reducing agent and (iminomethyl)ferrocenes and secondary (ferrocenylmethyl)amines by using LiAlH4. X-ray structures of representative members of these ferrocene derivative families have evidenced the preferred conformation adopted by ferrocene backbones, in which surprisingly the steric hindrance is apparently not systematically minimized. 15N NMR measurements on aminomethyl-substituted ferrocenes and derivatives are provided for the first time, establishing benchmark values ranging from -330 to -305 ppm (nitromethane δ 0 ppm). The cyclic voltammetry of these species evidences two clearly distinct oxidation potentials related to the iron(II) center and the amino function. These aminomethyl-substituted ferrocenes are potentially valuable for further ortho-directed functionalization of ferrocene.
- Dwadnia, Nejib,Allouch, Fatima,Pirio, Nadine,Roger, Julien,Cattey, Helene,Fournier, Sophie,Penouilh, Marie-Josee,Devillers, Charles H.,Lucas, Dominique,Naoufal, Daoud,Ben Salem, Ridha,Hierso, Jean-Cyrille
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p. 5784 - 5797
(2013/11/19)
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- On the properties of the anions derived from α-deprotonation of α-(o-carboran-1-yl)- and α-ferrocenyl-1-alkylbenzotriazoles
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The synthesis of 1-[(2-R-o-carboran-1-yl)methyl]benzotriazoles (R = Me, Ph) is described. α-Deprotonation of these compounds followed by reactions of the generated carbanions with MeI give the corresponding α-methylated products. Even at room temperature,
- Moiseev,Cherevatskaya,Verbitskaya,Glukhov,Peregudov,Kalinin
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p. 1933 - 1942
(2013/12/04)
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- Competitive condensation and tandem cyclization reactions of 2-cyano-3-ferrocenylacrylonitrile with amidines in an aqueous medium
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The synthesis of a series of ferrocenyl-substituted 2-aminopyridineand 6-amino-4,5-dihydropyridine-3,5-dicarbonitriles, 4-aminopyrimidine- and 3,4-dihydropyrimidine-5-carbonitriles by reactions of 2-cyano-3- ferrocenylacrylonitrile with amidines in aqueous medium is described. New fused 6-amino-2-ethoxy-4-ferrocenyl-5-ferrocenylmethyl-5-ferrocenyl methyl-4,5- dihydropyridine-3,5-dicarbonitrile was prepared in a tricomponent cyclodimerization from 2-cyano-3-ferrocenylacrylonitrile in presence of ethanol. The structures of the obtained compounds were established by IR, 1H and 13C NMR spectroscopy, mass-spectrometry and X-ray diffraction analysis.
- Klimova, Elena I.,Flores-Alamo, Marcos,Stivalet, Jose M. Mendez,Klimova, Tatiana
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p. 2505 - 2514
(2012/11/07)
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- Synthesis and structure of planar chiral ferroceno[d]pyridazinones, the first representatives of a novel class of fused metallocenes
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A series of planar chiral ferroceno[d]pyridazinones was prepared by hydrazine-mediated cyclisations of (Sp)-2-formylferrocenoyl fluoride obtained in two steps from (2S,4S)-4-(methoxymethyl)-2-ferrocenyl-1,3-dioxane. Further derivatives based on the novel heterocyclic scaffold were resulted by means of the facile N-alkylation reactions carried out on the easily accessible fused product derived from the hydrazine-mediated cyclisation. Upon treatment with hydrazine (Sp)-2-formylferroce carboxylic acid, the precursor of the acid fluoride with enhanced reactivity, afforded a dimeric azine avoiding cyclisation. The spectacular difference between the experimentally observed reactivity of the bifunctional formylferrocenes was disclosed by comparative DFT analysis of the assumed hydrazone- and hydrazide intermediates with different values of LUMO energy associated with different conformation. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC and DNOE measurements.
- Gy?m?re,Csámpai
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p. 1626 - 1631
(2011/05/06)
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- Influence of the substituent R1 on the reactivity of [(η5-C5H5)Fe{(η5-C 5H4)-CHN-(R1)-OH}] {R1 = -CH 2-CH2- or 1,2-C6H4} with platinum(ii) and on the properties of the complexes
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The synthesis and characterization of four different types of platinum(ii) complexes derived from [(η5-C5H5) Fe{(η5-C5H4)-CHN-(CH2-CH 2-OH)}] (1b) are reported. The new products are the trans- and cis-isomers of [Pt{(η5-C5H5) Fe[(η5-C5H4)-CHN-(CH2-CH 2-OH)]}Cl2(dmso)] {trans-(2b) and cis-(3b)} and the platinacycles [Pt{[(η5-C5H3)-CHN-(CH 2-CH2-OH)]Fe(η5-C5H 5)}Cl(L)] {with L = dmso (4b) or PPh3 (5b)} or [Pt{[(η5-C5H3)-CHN-(CH2-CH 2-O)]Fe(η5-C5H5)}(L)] {with L = PPh3 (6b) or dmso (7b)}. In these products 1b acts as a (N) donor ligand (in 2b and 3b), as a bidentate [C(sp2, ferrocene), N] - (in 4b and 5b) or as a terdentate [C(sp2, ferrocene), N, O]2- ligand (in 6b and 7b). The crystal structures of 4b and 5b confirm the mode of binding of the ferrocenylaldimine (1b) and a trans-arrangement between the neutral ligand (L) and the imine nitrogen. Comparative studies of: (a) the reactivity of ligands [(η5-C 5H5)Fe{(η5-C5H 4)-CHN-(R1)-OH}] {R1 = -CH2-CH 2- or 1,2-C6H4} with cis-[PtCl 2(dmso)2] and (b) the properties of their platinum(ii) complexes are also reported and provide conclusive evidence of the influence of the nature of the R1 group of [(η5-C5H 5)Fe{(η5-C5H4)-CHN-(R 1)-OH}] on: (a) the spectroscopic and electrochemical properties of these ligands and their platinum(ii) complexes, (b) the cycloplatination process, and (c) the ease with which the mode of binding of the ligand changes from bidentate [C(sp2, ferrocene), N]- to terdentate [C(sp2, ferrocene), N, O]2- or vice versa. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Lopez, Concepcion,Perez, Sonia,Solans, Xavier,Font-Bardia, Merce,Calvet, Teresa
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p. 676 - 685
(2010/06/18)
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- Specific features of oxidation of ferrocenylacetic acid with molecular oxygen in the absence and in the presence of Bronsted acids
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Comparative analysis of the specific features of autooxidation of ferrocenylacetic acid (FcCH2COOH) in organic solvents at 30-50°C in the absence and in the presence of trifluoroacetic acid (processes 1 and 2 respectively) was carried out. It w
- Fomin,Shirokov
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p. 2304 - 2316
(2010/04/29)
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