Archives for Chemistry Experiments of 1273-86-5

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The reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction. Safety of Ferrocenemethanol. In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

A surface-confined layer containing naphthoquinone was prepared by reacting 2,3-dichloronaphthoquinone with the amino tail groups of an aminoethanethiolate-modified vapor-deposited gold surface; this surface layer was then reacted with beta-ferrocenylethylamine. These modified gold electrodes were examined with cyclic staircase voltammetry in aqueous HClO4 at the completion of each step in this sequence of reactions. The voltammetric signature for the 2e-, 2H+ reduction of the quinoid redox centers disappeared after the ferrocene compound was reacted with the naphthoquinone surface layer; furthermore, the surface coverage of ferrocene was twice that expected on the basis of a 1:1 reaction between the surface-bound naphthoquinone and beta-ferrocenylethylamine. These results suggest that the latter reacts with the naphthoquinone carbonyl groups to form a surface-confined di-imine, which cannot be reduced within the electrochemical potential window of aqueous HClO4. In similar experiments, 2-[4?-(beta-ferrocenylethylaminocarbonyl)phenyl]-1,4-naphthoquinone and 2-[2?-(beta-ferrocenylethylaminocarbonyl)-ethyl]anthraquinone were synthesized and reacted with aminoethanethiolate-modified gold surfaces. When examined at a platinum electrode in nonaqueous solvents, both of the freely diffusing compounds exhibited two pairs of voltammetric waves characteristic of quinoid and ferrocene functionalities. However, only the ferrocene redox centers of the resulting surface-confined layers were electroactive, suggesting that the reaction of these compounds with the surface-confined aminoethanethiolate involves conversion of the quinoid carbonyls to imines.

A voltammetric investigation of the reactions between surface-confined amines and quinones on gold electrodes: Evidence for imine formation

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Reference:
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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Site-specific labelling of the cysteine-containing peptide glutathione with a ferrocene group was achieved by reaction with ferrocenylmethanol in aqueous acidic medium. The resulting peptide was shown to be a potent competitive inhibitor of the biologically important enzyme glutathione-(S)-transferase. This approach may prove general for the labelling of proteins with ferrocene. Site-specific labelling of the cysteine-containing peptide glutathione with a ferrocene group was achieved by reaction with ferrocenylmethanol in aqueous acidic medium. The resulting peptide was shown to be a potent competitive inhibitor of the biologically important enzyme glutathione-(S)-transferase. This approach may prove general for the labelling of proteins with ferrocene.

Site-selective and covalent labelling of the cysteine-containing peptide glutathione with a ferrocenyl group

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Reference:
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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A simple electrochemical approach was used to evaluate the stability and porosity of titania and silica thin films spin coated on electrode surfaces. This approach involved monitoring the magnitude of the Faradaic current of diffusing redox probes at the modified electrode surfaces over the course of a week to 4.5 months. Relatively nonporous films were examined as well as films templated with polystyrene latex spheres. The results show that templated titania films were significantly more porous compared to non-templated films. After the defect sites in the templated films were blocked, their long-term stability in aqueous electrolyte was evaluated. For titania, blocking was done by spin coating a dilute titania sol on the top of the film whereas for silica, the film was soaked in octyltrimethoxysilane. Both types of titania films (templated and non-templated) were found to be significantly more stable than the corresponding silica films, showing no signs of deterioration in simple electrolyte solutions during the entire evaluation period. In contrast, silica films showed significant deterioration in as little as 3 days. The enhanced stability of the titania films relative to silica films in near neutral electrolyte solutions was attributed to the differences in the point of zero charge of the oxide films.

The stability of nonporous and macroporous titania thin films in aqueous electrolyte solutions

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Reference:
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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Electrochemical molecularly imprinted polymers (e-MIPs) are reported for the first time. Their elaboration is based on the introduction of a redox tracer (vinylferrocene) inside the binding cavities of a cross-linked MIP. Determination of the analyte (benzo[a]pyrene) can be simply performed by measuring the redox tracer signal. the Partner Organisations 2014.

A versatile electrochemical sensing receptor based on a molecularly imprinted polymer

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Reference:
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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. SDS of cas: 1273-86-5. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

A sustainable and green route to access diverse functionalized ketones via dehydrogenative?dehydrative cross-coupling of primary and secondary alcohols is demonstrated. This borrowing hydrogen approach employing a pincer N-heterocyclic carbene Mn complex displays high activity and selectivity. A variety of primary and secondary alcohols are well tolerant and result in satisfactory isolated yields. Mechanistic studies suggest that this reaction proceeds via a direct outer-sphere mechanism and the dehydrogenation of the secondary alcohol substrates plays a vital role in the rate-limiting step.

Sustainable and Selective Alkylation of Deactivated Secondary Alcohols to Ketones by Non-bifunctional Pincer N-heterocyclic Carbene Manganese

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Reference:
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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Organometallic Ru(II)-cymene complexes linked to ferrocene (Fc) via nitrogen heterocycles have been synthesized and studied as cytotoxic agents. These compounds are analogues of Ru(II)-arene piano-stool anticancer complexes such as RAPTA-C. The Ru center was coordinated by pyridine, imidazole, and piperidine with 0-, 1-, or 2-carbon bridges to Fc to give six bimetallic, dinuclear compounds, and the properties of these complexes were compared with their non-Fc-functionalized parent compounds. Crystal structures for five of the compounds, their Ru-cymene parent compounds, and an unusual trinuclear compound were determined. Cyclic voltammetry was used to determine the formal MIII/II potentials of each metal center of the Ru-cymene-Fc complexes, with distinct one-electron waves observed in each case. The Fc-functionalized complexes were found to exhibit good cytotoxicity against HT29 human colon adenocarcinoma cells, whereas the parent compounds were inactive. Similarly, antibacterial activity from the Ru-cymene-Fc compounds was observed against Bacillus subtilis, but not from the unfunctionalized complexes. In both cases, the IC50 values correlated quantitatively with the Fc+/0 reduction potentials. This is consistent with more facile oxidation to give ferrocenium, and subsequent generation of toxic reactive oxygen species, leading to greater cytotoxicity. The antioxidant properties of the complexes were quantified by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. EC50 values indicate that linking of the Ru and Fc centers promotes antioxidant activity.

Activation by Oxidation: Ferrocene-Functionalized Ru(II)-Arene Complexes with Anticancer, Antibacterial, and Antioxidant Properties

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Reference:
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 bitopic ligand 1,1?-bis(dipyrazol-1-ylmethyl)ferrocene, Fe[C 5H4CH(pz)2]2 (1; pz = pyrazolyl ring), has been prepared by the reaction of 1,1?-ferrocenedicarbaldehyde and 1,1?-carbonyldipyrazole. In the solid state, the bis(pyrazolyl) methane moieties are in an antiperiplanar eclipsed orientation. The molecules are organized into a three-dimensional array by pi…pi, weak C-H-…N hydrogen bonding, and C-H…pi interactions. The reactions between 1 and AgBF4, AgPF6, AgSO3CF 3, or AgSbF6 yield {Fe[C5H 4CH(pz)2]2AgBF4}n (2), {Fe[C5H4CH(pz)2]2AgPF 6}n (3), {Fe[C5H4CH(Pz) 2]2AgSO3CF3}n (4), and {Fe[C5H4CH(pz2]2AgSbF 6}n (5), respectively. The solid-state structures consist of coordination polymers with compounds 2 and 3 arranged in helical chains, while the chains in 3·1/2Et2O, 4·1.5C6H 6,5·1/2Et2Et2O, and 5·1/2C 6H6 are nonhelical. In these structures, the ferrocenyl groups adopt a similar orientation, where the angle between CH(pz)2 groups is confined to the range of 85-99 and the silver pyrazolyl coordination spheres are also in very similar distorted-tetrahedral arrangements. Both structural types form three-dimensional supramolecular structures organized by weak hydrogen bonds, pi…pi stacking, and CH…pi interactions. In the helical form, the anions reside in the pockets formed by the close-packed chains, whereas in the nonhelical form, sizable channels, which contain the solvent molecules and the anions, are located between the chains.

Synthesis and Structural Characterization of a Bitopic Ferrocenyl-Linked Bis(pyrazolyl)methane Ligand and Its Silver(I) Coordination Polymers

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Reference:
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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Recommanded Product: 1271-51-8. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1271-51-8, Name is Vinylferrocene

X-ray absorption spectroscopy (XAS) was used to study the electrochemical incorporation of perrhenate anion, from a 0.1 M NH4ReO4 solution, into poly(vinylferrocene) (PVFc) and a modified PVFc (a copolymer of 30% t-butyl acetylferrocene and 70% t-butyl divinyl ferrocene). The polymers were deposited on a carbon cloth current collector from a solution of the polymers in CH2Cl2. In situ XAS measurements were done at the Fe K edge on the reduced polymers and at 0.9 V vs. Ag/AgCl. Ex situ XAS was done at the Re L3 edge after oxidation of the polymers at 0.9 V. The oxidized electrodes were washed in water to remove dissolved NH4ReO4 in the electrode pores. XAS was done both on wet-washed electrodes and on electrodes that were dried. XAS showed that at 0.9 V the Fe was oxidized from a ferrocene to a ferrocenium moiety and the Fe-C bond distance increased from 2.05 to 2.08 A. Both the X-ray absorption near-edge spectroscopy and extended X-ray absorption fine structure (EXAFS) results are consistent with having >75% of the ferrocene moieties in the polymer oxidized at 0.9 V. The Fe K-edge EXAFS showed no direct indication of interaction of Fe with ReO4-. At the Re L3 edge the only indication of interaction of ReO4- with the polymers was a slight change in the XANES features.

X-ray absorption studies of poly(vinylferrocene) polymers for anion separation

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Reference:
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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A dual-stream flow injection method has been developed for electrochemical detection of ferrocene derivatives in flow streams. The method is based on a previously described electrochemical amplification method in which currents for analyte oxidation are enhanced by rapid analyte regeneration via a solution-phase electron exchange reaction with a sacrificial reagent. The use of two independent flow channels in the present method, one to carry the analyte and another to supply the sacrificial reagent, eliminates the necessity of spiking samples and calibration standards with sacrificial reagent to avoid injection transients. Hydrodynamic voltammograms were recorded for a series of injections of hydroxymethylferrocene (HMFc, a model ferrocene analyte) into the carrier stream in the presence and absence of ferrocyanide (which serves as sacrificial reagent) in the reagent stream. From these voltammograms an optimum detection potential for HMFc of +0.8 V versus Ag|AgCl|KClsat was selected. Two different concentrations of sacrificial reagent were tested for a range of HMFc concentrations between 1 × 10-3 and 1 × 10-8 M for which both unamplified and amplified peaks could be detected. An amplification factor of approximately 300 was obtained for a 1 × 10-8 M HMFc injection with 2 × 10-4 M ferrocyanide present in the reagent stream.

Dual-stream flow injection method for amplified electrochemical detection of ferrocene derivatives

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Reference:
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 diiron bridging vinyliminium complexes [Fe2{mu- eta1:eta3-C=N(Me)2C(R?)=C(R?)} (mu-CO)(CO)(Cp)2][SO3CF3] (R? = H, R? = SiMe3, 3a; R? = H, R? = Tol =4-MeC 6H4, 3b; R? = Me, R? = Me, 3c; R? = SPh, R? = Me, 3d; R? = H, R? = Fc = [Fe(C5H 4)(Cp)], 6e) react with propargyl alcohol (HC?CCH 2OH), in refluxing toluene, affording the polysubstituted ferrocenes as mixtures of two isomeric forms: [1-NMe2-2-R?-3-R?-5- CH2OCH2C?CH-Fc] (R? = H, R? = SiMe 3, 6a; R? = H, R? = Tol, 6b; R? = Me, R? = Me, 6c; R? = SPh, R? = Me, 6d, R? = H, R? = Fc, 6e) and [1-NMe2-2-R?-3-R?-4-CH2OCH2C? CH-Fc] (R? = H, R? = SiMe3, 7a; R? = H, R? = Tol, 7b; R? = Me, R? = Me, 7c; R? = SPh, R? = Me, 7d) in overall yields of about 55-65%. Formation of the functionalized cyclopentadienyl in the ferrocene products takes place through the assembly of two propargyl units with the bridging vinyliminium ligand: one alkynol is incorporated by a [3 + 2] cycloaddition with the bridging C3 ligand; a second alkynol unit gives rise to a pendant chain through -OH substitution. Investigations show that the substitution step is catalyzed by the parent diiron complex itself or by a mononuclear iron fragment (likely the Fp+ complex). The pendant propargyl chain has been exploited to connect the ferrocene to other molecular fragments: in particular, the reaction of 6a with 4-biphenyl azide, by copper-catalyzed azide-alkyne cycloaddition (CuAAC), leads to the formation of the triazole-functionalized ferrocene [1-NMe 2-2-CH2OCH2-N3(C6H 4Ph)C2H-4-SiMe3-Fc] (12). Moreover, 6a reacts with Co2(CO)8, affording the complex [Co 2{mu-eta2-HC?CR}(CO)6] (13), (HC?CR = 6a), where the alkyne adopts a eta2 coordination to a dicobalt hexacarbonyl fragment. The molecular structure of 7a has been determined by X-ray diffraction studies.

Ferrocenes containing a pendant propargylic chain obtained via addition of propargyl alcohol to mu-vinyliminium ligands in diiron complexes

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Reference:
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