| Autor: |
Castillo CE; Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Instituto de Biomoléculas (INBIO), Universidad de Cádiz, Apartado 40, E-11510 Puerto Real, Cádiz, Spain. manuel.basallote@uca.es., Gonzálvez MA; Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, E-08028 Barcelona, Spain. manel.martinez@qi.ub.edu., Algarra AG; Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Instituto de Biomoléculas (INBIO), Universidad de Cádiz, Apartado 40, E-11510 Puerto Real, Cádiz, Spain. manuel.basallote@uca.es., Fernández-Trujillo MJ; Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Instituto de Biomoléculas (INBIO), Universidad de Cádiz, Apartado 40, E-11510 Puerto Real, Cádiz, Spain. manuel.basallote@uca.es., Ferrer M; Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, E-08028 Barcelona, Spain. manel.martinez@qi.ub.edu.; Institute of Nanoscience and Nanotechnology (IN2UB), Universitat de Barcelona, 08028 Barcelona, Spain., Martínez M; Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, E-08028 Barcelona, Spain. manel.martinez@qi.ub.edu.; Institute of Nanoscience and Nanotechnology (IN2UB), Universitat de Barcelona, 08028 Barcelona, Spain., Basallote MG; Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Instituto de Biomoléculas (INBIO), Universidad de Cádiz, Apartado 40, E-11510 Puerto Real, Cádiz, Spain. manuel.basallote@uca.es. |
| Abstrakt: |
The reaction of three [Fe II (TSC) 2 ] complexes, where TSC is a pyridine-substituted thiosemicarbazone of the HDpT or HBpT families, with H 2 O 2 in acetonitrile solution does not result in the accumulation of the corresponding [Fe III (TSC) 2 ] + complexes. Instead, a mixture of diamagnetic low-spin Fe II species is generated. According to the MS spectra, those species result from the sequential addition of up to five oxygen atoms to the complex. This capability for the addition of oxygen atoms suggested that oxygen atom transfer to external substrates may be possible, and these TSC complexes were tested in the oxidation of thioanisole and styrene with H 2 O 2 . As hypothesized, the complexes are active in both the oxidation of thioanisole to its sulfoxide and styrene to benzaldehyde, with time scales indicating the participation of the species containing added oxygen atoms. Interestingly, the free thiosemicarbazone ligands and the [Zn(Dp44mT) 2 ] complex also catalyse the selective sulfoxidation of thioanisole, but they are ineffective in catalysing styrene oxidation to benzaldehyde. These findings open up new directions for the development of thiosemicarbazone-based metal catalysts for oxidation processes. |
