0000000000019497
AUTHOR
María J. Sabater
showing 4 related works from this author
On the Existence of Different Zeolite-Associated Topological Redox Isomers. Electrochemistry of the Y Zeolite-Associated Mn(Salen)N3 Complex
2002
The electrochemical properties of Y zeolite-associated MnIII(salen)N3 (salen = trans-(R,R)-1,2-bis(salicyldeneamino)cyclohexane) has been investigated using polymer film electrodes immersed into neutral aqueous solutions. Zeolite Y-associated Mn(III)−salen complexes are reduced in one-electron reversible process at −0.25 V versus SCE. The electrochemical response is discussed in terms of the existence of two topological redox isomers: a weakly boundary-associated Mn(salen) complex, whose electrochemical response corresponds to a reversible one-electron transfer controlled by diffusion of the positive ions of the supporting electrolyte through the zeolite surface windows and channels, and a…
Competition between decarboxylation and isomerization in the C3H5O 2+ energy surface. Justification of the experimental results by molecular orbital …
1994
In constrast with recent molecular orbital calculations on the decarboxylation of O-protonated 2-oxetanone, this experimental work indicates that no decarboxylation of this cation occurs in sulphuric acid solution up to 150°C, but instead a clean isomerization to protonated acrylic acid takes place. Parallel theoretical work shows that the gas-phase model is too crude to account successfully for the experimental facts obtained in acidic media. However, the latter are well reproduced when the effect of the solvent is taken into account. The present findings do not necessarily invalidate the reaction mechanism currently accepted to explain the rate enhancement and change of stereochemistry ac…
Electrochemical Analysis of Catalytic and Oxygen Interfacial Transfer Effects on MnO2 Deposited on Gold Electrodes
2018
[EN] A theoretical model for obtaining thermochemical and kinetic information on oxygen interfacial transfer in metal oxides deposited on gold electrodes, based in the voltammetry of immobilized particle methodology, is presented. It is applied to MnO2 microparticulate deposits on gold in contact with aqueous NaOH solution using the voltammetric signals for the oxidation of gold to gold oxide monolayer and its subsequent desorptive reduction. Assuming reversibility, voltammetric peak potentials permit to estimate a variation of Gibbs free energy of interfacial oxygen transfer of -32 +/- 3 kj mol(-1). Analysis of peak current data based on the Sharp-Hancock formalism of solid-state kinetics …
Enantioselective epoxidation of olefins with molecular oxygen catalyzed by gold(III): A dual pathway for oxygen transfer
2009
Abstract A chiral gold(III) complex has been prepared that performs the epoxidation of olefins in the presence of O 2 , PhIO, or bleach. Catalytic experiments with 18 O show that O 2 is activated on the catalyst and can be directly incorporated into the epoxide through a non-radical mechanism that probably involves formation of gold, oxo, or peroxo species. In addition to this, there is a parallel radical mechanism operating that yields α , β -unsaturated ketones and alcohols as subproducts. Electrochemical and UV–Vis experiments confirmed the occurrence of a Au(III)/Au(I) redox cycle during the catalytic epoxidation in a mechanism sustained by molecular oxygen.