title: Lanthanum(III)-catalyzed disproportionation of hydrogen peroxide: a heterogeneous generator of singlet molecular oxygen-1O2 (1Deltag)-in near-neutral aqueous and organic media for peroxidation of electron-rich substrates.
abstract: The decomposition of hydrogen peroxide into singlet molecular oxygen-(1)O(2) ((1)Delta(g))-in the presence of lanthanum(iii) salts was studied by monitoring its characteristic IR luminescence at 1270 nm. The process was found to be heterogeneously catalyzed by La(III), provided that the heterogeneous catalyst is generated in situ. The yield of (1)O(2) generation was assessed as 45+/-5 % both in water and in methanol. The pH-dependence on the rate of (1)O(2) generation corresponds to a bell-shaped curve from pH 4.5 to 13 with a maximum around pH 8. The study of the influence of H(2)O(2) showed that the formation of (1)O(2) begins as soon as one equivalent of H(2)O(2) is introduced. It then increases drastically up to two equivalents and more smoothly above. Unlike all other metal salt catalyst systems known to date for H(2)O(2) disproportionation, this chemical source of (1)O(2) is able to generate (1)O(2) not only in basic media, but also under neutral and slightly acidic conditions. In addition, this La-based catalyst system has a very low tendency to induce unwanted oxygenating side reactions, such as epoxidation of alkenes. These two characteristics of the heterogeneous lanthanum catalyst system allow non-photochemical (i.e., "dark") singlet oxygenation of substrate classes that cannot be peroxidized successfully with conventional molybdate catalysts, such as allylic alcohols and alkenyl amines.
authors.affiliation: LCOM, Equipe de Recherches "Oxydation et Formulation" UMR CNRS 8009, ENSCL BP 108 59652 Villeneuve d'Ascq Cedex, France.
authors.forename: Véronique
authors.initials: V
authors.lastname: Nardello
authors.forename: Jacques
authors.initials: J
authors.lastname: Barbillat
authors.forename: Jean
authors.initials: J
authors.lastname: Marko
authors.forename: Peter T
authors.initials: PT
authors.lastname: Witte
authors.forename: Paul L
authors.initials: PL
authors.lastname: Alsters
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Aubry