Article

Transition Metal Chemistry

, Volume 38, Issue 2, pp 119-127

Dioxygen activation in photooxidation of diphenylmethane by a dioxomolybdenum(VI) complex anchored covalently onto mesoporous titania

  • Nelson J. CastellanosAffiliated withFacultad de Química Ambiental, Grupo de Investigaciones Ambientales para el desarrollo Sostenible-GIADS, Universidad Santo TomasEscuela de Química, Centro de Investigación en Catálisis-CICAT, Universidad Industrial de SantanderDepartment of Inorganic and Physical Chemistry, Centre for Ordered Materials, Organometallics and Catalysis-COMOC, University of Ghent Email author 
  • , Fernando MartínezAffiliated withEscuela de Química, Centro de Investigación en Catálisis-CICAT, Universidad Industrial de Santander
  • , Frédéric LynenAffiliated withLaboratory of Separation Sciences, Department of Organic Chemistry, University of Ghent
  • , Shyam BiswasAffiliated withDepartment of Inorganic and Physical Chemistry, Centre for Ordered Materials, Organometallics and Catalysis-COMOC, University of Ghent
  • , Pascal Van Der VoortAffiliated withDepartment of Inorganic and Physical Chemistry, Centre for Ordered Materials, Organometallics and Catalysis-COMOC, University of Ghent
  • , Henri ArzoumanianAffiliated withChirosciences UMR CNRS 7313 Institut des Sciences Moléculaires de Marseille (iSm2), Aix-Marseille Université Email author 

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Abstract

A dioxomolybdenum(VI) complex has been covalently anchored onto mesoporous titania by a silicon-assisted transesterification route. The grafting of the complex to the mesoporous structure was confirmed by diffuse reflectance infrared Fourier transform, Raman and UV–Vis spectroscopy and by nitrogen sorption experiments. The ability of the grafted complex to activate molecular oxygen (O2) has been evaluated in the photooxidation of diphenylmethane to produce benzophenone. The photooxidation of diphenylmethane was monitored continuously by in situ dispersive Raman spectroscopy. A scheme for the activation of molecular oxygen under very mild conditions is proposed. A comparison with the same complex anchored onto commercial titanium P-25 and silica gel revealed both the beneficial effect of the mesoporous structure and the existence of a synergistic effect between MoO/TiO2/O2/light entities, which promotes the photooxidation process under green chemistry conditions. Finally, the heterogeneous catalyst is sustainable; it can be recycled and reused without significant loss in activity or selectivity.