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Electrical current oscillations in vapor-adsorbed ferrocene derivatives having two substituted groups

Oscillations in electrical current as a function of time have been observed in a specific temperature range in the samples of 1,1?-diacetylferrocene and 1,1?-ferrocenedicarboxylic acid with adsorbed ethanol vapor in a sandwich-type cell. The frequency of current oscillations has been found to decrease with bias voltage and sample temperature and to increase with vapor pressure. The frequency of current oscillations for the mono-group substituted derivatives is higher than the corresponding frequency for the derivatives having two substituted groups. Again, the frequency of oscillations for -COCH3 group substituted derivatives is higher than the corresponding value for -COOH group substituted derivatives. The observation of current oscillations is possibly associated with some kind of time dependent phase changes, arising from the structural nonrigidity of the molecules, in the solid-ethanol vapor system at the sample surface layer. The “ball-bearing” motion of the cyclopentadienyl rings of ferrocene unit, nature and number of substituted groups, cooperative interaction of the neighboring molecules influence the structural nonrigidity and hence the oscillatory behavior of current. Reasons are given for ruling out other models of current oscillations in semiconductors.

Electrical current oscillations in vapor-adsorbed ferrocene derivatives having two substituted groups

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The ferrocene derivative containing nitrogen-oxygen free radical method of preparation and use thereof (by machine translation)

The invention discloses a novel containing nitrogen oxygen free radical ferrocene derivatives preparation method and use thereof, of formula (I) is shown containing nitrogen oxygen free radical of the ferrocene derivative or its pharmaceutically acceptable salt or pharmaceutical composition or solvate. (I) in formula (I) indicated by the ferrocene derivative to a lung cancer cell strain A549 and breast cancer cell MCF – 7 of value-added has very strong inhibiting activity, can be used as a medicine for treating cancer, tumor diseases such as candidate compound or a lead compound. (by machine translation)

The ferrocene derivative containing nitrogen-oxygen free radical method of preparation and use thereof (by machine translation)

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Substituent effects in the iron 2p and carbon 1s edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy of ferrocene compounds

The iron 2p and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of substituted ferrocene compounds (Fe(Cp-(CH3) 5)2, Fe(Cp)(Cp-COOH), Fe(Cp-COOH)2, and Fe(Cp-COCH3)2) are reported and are interpreted with the aid of extended Hiickel molecular orbital (EHMO) theory and density functional theory (DFT). Significant substituent effects are observed in both the Fe 2p and C 1s NEXAFS spectra. These effects can be related to the electron donating/withdrawing properties of the cyclopentadienyl ligands and their substituents as well as the presence of pi* conjugation between the cyclopentadienyl ligand and unsaturated substituents.

Substituent effects in the iron 2p and carbon 1s edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy of ferrocene compounds

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

The important role of 1,1′-Ferrocenedicarboxaldehyde

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Simple reduction of ferrocenyl aldehydes and ketones by sodium boranuide in trifluoroacetic acid: New, efficient, general preparation of alkylferrocenes

Alkylferrocenes are obtained in excellent yields by ionic hydrogenation of ferrocenyl aldehydes and ketones using sodium boranuide and trifluoroacetic acid.

Simple reduction of ferrocenyl aldehydes and ketones by sodium boranuide in trifluoroacetic acid: New, efficient, general preparation of alkylferrocenes

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

Extracurricular laboratory:new discovery of Vinylferrocene

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Kinetics of the synthesis of the S-(1-ferrocenylethyl)thioglycolic acid

A systematic study of the reactions of a number of alpha-hydroxylated ferrocene derivatives with thioglycolic acid confirms that the reaction is extremely fast, viz., 15-20 min <1>, as compared with earlier procedures (12 h) <2,3>.The important kinetic parameters of the reaction of 1-ferrocenylethanol with the thioglycolic acid in the presence of trifluoroacetic acid have been determined.

Kinetics of the synthesis of the S-(1-ferrocenylethyl)thioglycolic acid

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

Final Thoughts on Chemistry for 1271-51-8

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Efficient thiol-yne click chemistry of redox-active ethynylferrocene

The application of ethynylferrocene, FcCCH (1), as a highly efficient electroactive precursor for the thiol-yne click reaction is presented. For this purpose, a wide range of functionalized thiols, namely 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropionic acid, 4-aminothiophenol, and benzene-1,3-dithiol as well as tetrathiol pentaerythritol tetrakis(3-mercaptopropionate), were investigated. This facile thiol-ethynylferrocene radical reaction has resulted in the quantitative formation and isolation of the newly ferrocenyl-vinyl sulfides FcCH=CHS(CH2)2OH (2Z and 2E), FcCH=CHSCH2CH(OH)CH2OH (3Z and 3E), FcCH=CHS(CH2)2COOH (4Z and 4E), FcC(CH2)S(1,4-C6H4)NH2 (5alpha), FcCH=CHS(1,3-C6H4)SCH=CHFc (6), and [FcCH=CHS(CH2)2COOCH2]4C (7). Thiol-ethynylferrocene reactions have been initiated either by heat, in toluene with AIBN, or by UV light irradiation in THF in the presence of DMPA as photoinitiator. The outcome of the hydrothiolation of ethynylferrocene strongly depends on the thiol structure and on the initiation method employed. A simple mixing of metallocene 1 with the thiol HS(CH2)2OH or HS(CH2)2COOH in a proper ratio, in THF at 20 C, in a initiator-free thiol-yne reaction, causes hydrothiolation of 1 to occur, allowing for the formation of vinyl sulfides 2Z, 2E and 4Z, 4E in good isolated yields. In contrast to the bis-addition typically observed for thiol-yne reactions, no double hydrothiolation to FcCCH has been observed for any of the thiols under any conditions studied. Electrochemical studies showed that tetrametallic compound 7, containing four sulfur-bridged ferrocenyl-vinyl moieties, behaves as a tetrapodal adsorbate molecule, exhibiting excellent chemisorption properties, and spontaneously forms robustly adsorbed 7 films onto Au or Pt electrode surfaces.

Efficient thiol-yne click chemistry of redox-active ethynylferrocene

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The substitution chemistry of the tris(3,5-dimethylpyrazolyl)-methanerhodium complex [Rh(CO)2{HC(pz?)3}]+

The complex [Rh(CO)2{HC(pz?)3}][PF6], 1 +[PF6]- {HC(pz?)3 = tris(3,5-dimethylpyrazolyl)methane}, prepared by reacting [{Rh(CO)2(mu-Cl)}2] with HC(pz?)3 in the presence of Tl[PF6], has a distorted square pyramidal structure with a kappa3-HC(pz?)3 ligand. Carbonyl substitution with Lewis bases gives [Rh(CO)L{HC(pz?)3}] [PF6] {L = PPh3, 2+[PF6]-; L = AsPh3, 3+[PF6]-; L = P(o-tolyl)3, 4+[PF6]-}, which have square planar kappa2 structures, confirmed by X-ray crystallography for 2+[PF6]-. The cations 2+ and 3+ have the third pyrazolyl ring orientated pseudo-parallel to the square planar metal whereas 4+ more likely has the third ring orientated exo to that plane. One-electron oxidation of 2+ and 3+ gives the Rh(II) dications [Rh(CO)(PPh3){HC(pz?)3}]2+, 22+, and [Rh(CO)(AsPh3){HC(pz?)3}]2+, 32+, characterised by ESR spectroscopy. Complex 1+[PF6]- reacts with PhC?CPh to give [Rh(CO)(eta2-PhC?CPh)-{HC(pz?)3}] [PF6], 5+[PF6]-, in which the two-electron donor alkyne occupies an equatorial position in a trigonal bipyramidal kappa3 structure. With MeC?CR (R = Me or Et), 1+[PF6]- gives the kappa2 square planar complexes [Rh{eta4-C4Me2R2C(O)}{HC(pz? )3}][PF6] (R = Me, 6+[PF6]-; R = Et, 7+[PF6]-) in which the cyclopentadienone ligands are coordinated via two Rh-monoalkene bonds; the structurally characterised form of 7+ has the two alkyne units linked head-to-head with the CEt termini bound to the ketonic CO group. With HC?CPh or HC?CH, 1+ gives the octahedral, kappa3 rhodium(III) metallacyclopentadienes [Rh(CO)(eta1:eta1?-CHCRCHCR) {HC(pz?)3}][PF6] (R = Ph, 8+[PF6]-; R = H, 9+[PF6]-) with the two alkynes linked head-to-tail in 8+. The reaction of 1+ with HC?CH also gives the cycloheptatrienone (tropone) derivative [Rh{eta4-C6H6C(O)}{HC(pz?)3} ][PF6], 10+[PF6]-, with a kappa3 ligand and the cycloheptatrienone ligand bound to the metal via two Rh-C sigma-bonds and one Rh-monoalkene interaction.

The substitution chemistry of the tris(3,5-dimethylpyrazolyl)-methanerhodium complex [Rh(CO)2{HC(pz?)3}]+

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

Brief introduction of Vinylferrocene

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Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds

Reactions of Cp2TiMe2, with the ester derivatives of organometallic sandwich compounds (n5-RC5H4)Fe(n5-C5H5) and (n5-RC5H4)Co(n4-C4Ph4) (R=ester groups) gave products having R=C(CH2)Me, instead of the expected vinyl ethers indicating conversion of the ester units by Cp2TiMe2 to methyl ketones followed by methylenation. A reaction of Cp2TiMe2 with the diester (n5-RC5H4)Co(n4-C4Ph3R)(R=C(O)OMe) also gave similar results. The study has also been successfully extended to metal sandwich derived amides, thio and seleno esters. By controlling the amount of Cp2TiMe2, the reactions were also stopped at the methyl ketone stage and the methyl ketones were isolated in good yields and characterized. The method provides an easy and direct access to convert organometallic sandwich derived esters and related compounds to 1-methylvinyl derived products.

Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

Archives for Chemistry Experiments of Vinylferrocene

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H2-Acceptorless Dehydrogenative Boration and Transfer Boration of Alkenes Enabled by Zirconium Catalyst

The first example of an efficient and direct dehydrogenative boration of alkenes for vinyl boronate ester synthesis was achieved using a zirconium catalyst. Our methodology avoids using precious transition metals, additional hydrogen acceptors, high temperatures, and long reaction times, which were required to overcome the reducing ability of borane, to give alkyl boronate esters. Detailed mechanistic studies revealed a reversible reaction pathway and further suggested applying the zirconium complex as a ?shuttle catalyst? for transfer boration, which thus sidesteps the use of relatively sensitive borane.

H2-Acceptorless Dehydrogenative Boration and Transfer Boration of Alkenes Enabled by Zirconium Catalyst

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Novel anticancer and antibacterial organometallic polymer based on ferrocene as a building block and xanthone bioactive scaffolds: Synthesis, characterization, and biological study

Poly(azine ferrocene-triazole-xanthone amide) (PAFTXA) was successfully synthesized from azine ferrocene bisacetylene (AFcB) and 2,7-(N-2-azidoacetamide) xanthone (NAzX) by using click chemistry protocol. In this paper, innovative AFcB moiety incorporated in this procedure as a monomer. This monomer was prepared in three steps from ferrocene scaffold, and the synthetic processes were discussed in details. Characterization of the synthesized novel intermediate materials, monomer, and the resulting polymer was performed by nuclear magnetic resonance, Fourier transform infrared, thermal gravimetric analysis, differential scanning calorimetry, and ultraviolet-visible spectrophotometer. In addition, the in vitro antibacterial activity of the polymer was appraised against Gram-positive and Gram-negative bacteria by using minimum inhibitory concentration method. Moreover; antitumoral effects of synthesized polymer were evaluated on Hela, MCF-7, and Saos cancer cell lines and compared with normal fibroblast cell line by means of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. Promising antiproliferative effects were detected on both epitheloid and mesenchymal cancer cell lines depending on PAFTXA concentration and time. Survey on its characteristic features revealed the proficiencies of our prepared biomaterial such as its high thermal stability as well as valuable antitumoral and antibacterial capabilities that make it an appreciable candidate for further bioapplications.

Novel anticancer and antibacterial organometallic polymer based on ferrocene as a building block and xanthone bioactive scaffolds: Synthesis, characterization, and biological study

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion