Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide

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The activity of complex heteropolytungstates of general formula B-α- [MII4(H2O)2(PW9O34)2]10- (1) with M= Co(II), Zn(II), Mn(II) and Cu(II) (PWM) was investigated in the selective oxidation reaction of diphenylsulfide to diphenylsulfoxide in presence of tert-butylhydroperoxide as oxidant. The charac...

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Autores principales: Egusquiza, María Gabriela, Ben Tayeb, Karima, Muñoz, Mercedes, Romanelli, Gustavo Pablo, Cabello, Carmen Inés, Botto, Irma Lía, Thomas, Horacio Jorge
Formato: Articulo
Lenguaje:Inglés
Publicado: 2009
Materias:
Química
heteropolytungstates
diphenylsulfoxides
selective oxidation
tert-butyl-hydroperoxide
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/177404
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-177404
record_format dspace
spelling I19-R120-10915-1774042025-03-14T20:12:03Z http://sedici.unlp.edu.ar/handle/10915/177404 Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide Egusquiza, María Gabriela Ben Tayeb, Karima Muñoz, Mercedes Romanelli, Gustavo Pablo Cabello, Carmen Inés Botto, Irma Lía Thomas, Horacio Jorge 2009 2025-03-14T16:58:21Z en Química heteropolytungstates diphenylsulfoxides selective oxidation tert-butyl-hydroperoxide The activity of complex heteropolytungstates of general formula B-α- [MII4(H2O)2(PW9O34)2]10- (1) with M= Co(II), Zn(II), Mn(II) and Cu(II) (PWM) was investigated in the selective oxidation reaction of diphenylsulfide to diphenylsulfoxide in presence of tert-butylhydroperoxide as oxidant. The characterization of phases was performed by X Ray Powder Diffraction, XRD. All phases resulted isomorphous although PWCu is obtained as a mixture of two structural isomers [Cu2(H2O)2PW10O38]7-.The oxidation reaction was carried out in batch at 80°C using toluene as solvent and t-butylhydroperoxide 5-6 M in decane as oxidant for 6 h. The catalytic evaluation made by gas chromatography revealed a similar behavior with conversions of diphenylsulfide around 60% and high selectivity to diphenylsulfoxide near to 95% for most of phases studied while PWCu resulted the most active catalyst presenting a conversion of 84%. The activity rise was correlated with the increase of the oxidant character of the cluster metal(II). Se investigó la actividad de heteropolitungstatos complejos de fórmula general B-α- [MII4(H2O)2(PW9O34)2]10- (PMW) con M= Co(II), Zn(II), Mn(II) y Cu(II) en la reacción de oxidación selectiva de difenilsulfuro a difenilsulfóxido en presencia de peróxido de ter-butilo como oxidante. La caracterización de las fases se realizó por Difracción de Polvos por Rayos X, DRX. El estudio mostró que a excepción del precursor y la fase conteniendo MII4 Cu(II), las fases con M4 = Co(II), Zn(II) y Mn(II) son isomorfas. La fase correspondiente a Cu(II) se obtiene como componente de una mezcla conteniendo además dos isómeros estructurales de fórmula [Cu2(H2O)2PW10O38]7-. La reacción de oxidación se llevó a cabo en batch a 80°C en tolueno como solvente y peróxido de t-butilo como oxidante, durante un período de 6 h. La evaluación catalítica realizada por cromatografía gaseosa reveló un comportamiento similar con conversiones de difenilsulfuro alrededor del 60% y una alta selectividad a difenilsulfóxido no menor al 95% para la mayoría de las fases estudiadas mientras que el sistema que contiene cobre con M(II) = Cu resultó el catalizador más activo presentando una conversión de 84%. El incremento en la actividad se correlaciona con el incremento del carácter oxidante del metal del cluster. Centro de Investigación y Desarrollo en Ciencias Aplicadas Centro de Química Inorgánica Articulo Articulo http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) application/pdf 166-173
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
heteropolytungstates
diphenylsulfoxides
selective oxidation
tert-butyl-hydroperoxide
spellingShingle Química
heteropolytungstates
diphenylsulfoxides
selective oxidation
tert-butyl-hydroperoxide
Egusquiza, María Gabriela
Ben Tayeb, Karima
Muñoz, Mercedes
Romanelli, Gustavo Pablo
Cabello, Carmen Inés
Botto, Irma Lía
Thomas, Horacio Jorge
Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide
topic_facet Química
heteropolytungstates
diphenylsulfoxides
selective oxidation
tert-butyl-hydroperoxide
description The activity of complex heteropolytungstates of general formula B-α- [MII4(H2O)2(PW9O34)2]10- (1) with M= Co(II), Zn(II), Mn(II) and Cu(II) (PWM) was investigated in the selective oxidation reaction of diphenylsulfide to diphenylsulfoxide in presence of tert-butylhydroperoxide as oxidant. The characterization of phases was performed by X Ray Powder Diffraction, XRD. All phases resulted isomorphous although PWCu is obtained as a mixture of two structural isomers [Cu2(H2O)2PW10O38]7-.The oxidation reaction was carried out in batch at 80°C using toluene as solvent and t-butylhydroperoxide 5-6 M in decane as oxidant for 6 h. The catalytic evaluation made by gas chromatography revealed a similar behavior with conversions of diphenylsulfide around 60% and high selectivity to diphenylsulfoxide near to 95% for most of phases studied while PWCu resulted the most active catalyst presenting a conversion of 84%. The activity rise was correlated with the increase of the oxidant character of the cluster metal(II).
format Articulo
Articulo
author Egusquiza, María Gabriela
Ben Tayeb, Karima
Muñoz, Mercedes
Romanelli, Gustavo Pablo
Cabello, Carmen Inés
Botto, Irma Lía
Thomas, Horacio Jorge
author_facet Egusquiza, María Gabriela
Ben Tayeb, Karima
Muñoz, Mercedes
Romanelli, Gustavo Pablo
Cabello, Carmen Inés
Botto, Irma Lía
Thomas, Horacio Jorge
author_sort Egusquiza, María Gabriela
title Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide
title_short Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide
title_full Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide
title_fullStr Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide
title_full_unstemmed Potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide
title_sort potentiality of heteropolytungstates as catalysts in the selective oxidation of diphenylsulfide to diphenylsulfoxide
publishDate 2009
url http://sedici.unlp.edu.ar/handle/10915/177404
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