Search results for "Redox"
showing 10 items of 619 documents
ChemInform Abstract: Merging Visible-Light-Photoredox and Nickel Catalysis
2015
Review: [scope and limitations of the combination of nickel and photoredox catalysis for Csp3—Csp2 cross-coupling reactions; 18 refs.
Mössbauer Study of Lanthanum–Strontium Ferromanganite Oxides
2004
The La0.88Sr0.2Mn(1−y)Fey0(3±δ, i (LSMF with y = 0, 0.2, 0.5, 0.8, 1) compounds are prospective cathode materials for advanced solid oxide fuel cells (SOFC) application operating at 700° C. Usual analysis methods like thermogravimetric analysis or redox titration enable to determine the average oxidation state of both manganese and iron cations. The comparative role of iron and manganese in B-site was evaluated by 57Fe Mossbauer spectroscopy. Spectra revealed that the complete substitution of iron for manganese induces the formation of Fe5+ for the compound with y = 1. However, no tetravalent iron cation was observed in air for the LSMF compounds with y = 0.2, 0.5 and 0.8. This means that o…
Source of Selectivity in Oxidative Cross-Coupling of Aryls by Solvent Effect of 1,1,1,3,3,3-Hexafluoropropan-2-ol
2015
Abstract Solvents such as 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) with a high capacity for donating hydrogen bonds generate solvates that enter into selective cross-coupling reactions of aryls upon oxidation. When electric current is employed for oxidation, reagent effects can be excluded and a decoupling of nucleophilicity from oxidation potential can be achieved. The addition of water or methanol to the electrolyte allows a shift of oxidation potentials in a specific range, creating suitable systems for selective anodic cross-coupling reactions. The shift in the redox potentials depends on the substitution pattern of the substrate employed. The concept has been expanded from arene-phenol…
ChemInform Abstract: Source of Selectivity in Oxidative Cross-Coupling of Aryls by Solvent Effect of 1,1,1,3,3,3-Hexafluoropropan-2-ol.
2016
Abstract Solvents such as 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) with a high capacity for donating hydrogen bonds generate solvates that enter into selective cross-coupling reactions of aryls upon oxidation. When electric current is employed for oxidation, reagent effects can be excluded and a decoupling of nucleophilicity from oxidation potential can be achieved. The addition of water or methanol to the electrolyte allows a shift of oxidation potentials in a specific range, creating suitable systems for selective anodic cross-coupling reactions. The shift in the redox potentials depends on the substitution pattern of the substrate employed. The concept has been expanded from arene-phenol…
A crucial role of adamantanoid Cu(II) complexes in the redox systems: CuCl–diallylsulfoxide–O2 and CuCl2–diallylsulfide–O2
2014
Abstract The hypothetically reversible [Cu(I)(diallylsulfoxide)] ↔ O 2 [Cu(II)(diallylsulfide)] system was examined by FTIR spectroscopy and X-ray diffraction. It is stated that the Cu4OCl6 body centered adamantanoid cages, appearing at both the substrate and product sites, act as a template to promote the oxidation of diallylsulfide to diallylsulfoxide or Cu(I) to Cu(II), thus making the reaction irreversible. Each of these two adamantanoid cores possesses a different point symmetry as well as self assembly mode to form two polymorphs of the [Cu4OCl6(diallylsulfoxide)4] complex. Their polymorphic relationships based on the symmetry homology S4 ← Td → C3, as well as the distortion in the Cu…
Synthesis and Oxidant Properties of Phase 1 Benzepine N-Oxides of Common Antipsychotic Drugs
2013
There is increasing evidence that cell constituents are oxidized by widely used antipsychotic drugs but until now the underlying chemistry has remained unclear. It is well known that such drugs readily undergo N-oxidation as a first key metabolic step. To gain insight into the problem, the tertiary phase 1 N-oxides of clozapine, olanzapine, quetiapine, and zotepine were synthesized, together with the N,S-dioxides of quetiapine and zotepine. These N-oxides were then subjected to well-established chemical transformations to test their oxidant properties in group VIII transition-metal-catalyzed reactions. In the osmium tetroxide catalyzed dihydroxylation of styrene or cinnamyl alcohol and in …
Crystallization of late-stage MORB under varying water activities and redox conditions: Implications for the formation of highly evolved lavas and ox…
2018
Abstract In order to understand late magmatic processes that occur in the deep oceanic crust, we performed a phase-equilibria study in a representative late-stage system at a pressure of 200 MPa with a special focus on the role of water and oxygen fugacity. The starting composition for the experiments was evaluated based on a statistical approach using evolved fresh MORB glasses from the database PETDB highest in FeO and TiO2 (in average 17.92 wt% and 3.73 wt%, respectively), assumed to represent frozen liquids erupted at the seafloor generated by extensive differentiation of MORB. We conducted crystallization experiments in a range of temperatures from 850 to 1050 °C with water activities …
Technical and economical assessment of distributed electrochemical storages for load shifting applications: An Italian case study
2016
Time-of-use (TOU) energy cost management involves the use of energy storage systems (ESSs) by customers to reduce their electricity bills. The ESS is charged during off-peak time periods, when electricity energy prices are low, and discharged during times when on-peak energy prices are applied. This article addresses the question whether it is economically viable to install medium-scale distributed ESSs designed to lower the electricity cost for a customer-side application, assuming flexible electricity tariffs. The technical/economical evaluation is carried out referring to lithium-ion (Li-ion), sodium sulfur (NaS) and vanadium redox battery (VRB) technologies, performing a parametric anal…
Thermodynamics of competing oxidation reactions of allyl methyl disulfide by hydrogen peroxide: a first principle molecular computational study on th…
2008
Allyl methyl disulfide, a peroxide scavenger, was studied together with three isomeric (two sulfoxides and one epoxide) forms of its mono-oxidized products. After a full conformational study of the reactant and three isomeric oxidized forms, the geometries were optimized at B3LYP/6-31G (d) level of theory. The epoxide form turned and to be more stable than either one of the two isomeric sulfoxides. Changes for Thermodynamic functions of oxidation reactions were calculated and from the δGreaction values the equilibrium constant for the interconversions of the oxidized products were estimated. Bader-type AIM analyses were performed on the electron density, computed at the B3LYP/6-311++G (d,p)…
Photoinduced molecular rearrangements. The photochemistry of 1,2,4-oxadiazoles in the presence of sulphur nucleophiles. Synthesis of 1,2,4-thiadiazol…
1997
Abstract The photochemistry of some 1,2,4-oxadiazoles in the presence of sulphur nucleophiles has been investigated. Irradiation of the 5-amino-3-phenyl- and 3,5-diphenyl-1,2,4-oxadiazole at γ = 254 nm in methanol in the presence of sodium hydrogen sulphide or thiols gave a photo-induced redox reaction at the ring ON bond, leading to the corresponding N -substituted benzamidines. By contrast, irradiation of the 5-amino-3-phenyl-1,2,4-oxadiazole in the presence of thioureas or thiocarbamates, essentially gave 3-phenyl-5-substituted 1,2,4-thiadiazoles, which presume an NS bond formation between the ring-photolytic species and the sulphur nucleophile. In turn, irradiation of the same 5-amino…