CONICET | Buscador de Institutos y Recursos Humanos

ABSTRACT: The reaction of 5-alkylthio-3H-1,2-dithiole-3-thione derivatives with Fischer alkoxy carbenes gives 1,3- dithiin dithioorthoesters derivatives complexed with M(CO)5 (M¼Cr or W).We report here that the dithiin derivative free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. dithiin dithioorthoesters derivatives complexed with M(CO)5 (M¼Cr or W).We report here that the dithiin derivative free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. dithiin dithioorthoesters derivatives complexed with M(CO)5 (M¼Cr or W).We report here that the dithiin derivative free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. H-1,2-dithiole-3-thione derivatives with Fischer alkoxy carbenes gives 1,3- dithiin dithioorthoesters derivatives complexed with M(CO)5 (M¼Cr or W).We report here that the dithiin derivative free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. 5 (M¼Cr or W).We report here that the dithiin derivative free of metal can be obtained b ligand exchange using acetonitrile, methanol, phenyl methyl sulfide or (Ph)3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. 3P. Methanol gives the best results from a preparative point of view. The reaction with acetonitrile was shown to be reversible and the kinetic of ligand exchange and the activation parameters were determined. From these data it is concluded that the mechanism is predominantly dissociative forM¼Cr and it has some contribution of the associative mechanism for M¼W. mechanism for M¼W. mechanism for M¼W. ¼Cr and it has some contribution of the associative mechanism for M¼W.¼W.