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

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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.

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Acknowledgments

Part of this work was performed under the auspices of a COOPEN program funded by the European Community. N.J.C. is grateful to COLCIENCIAS “Fondo de Apoyo a los Doctorados Nacionales.” The Raman instrument is funded by the Ghent University, GOA grant Nr. 01G00710.

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Authors and Affiliations

  1. Facultad de Química Ambiental, Grupo de Investigaciones Ambientales para el desarrollo Sostenible-GIADS, Universidad Santo Tomas, Campus Universitario Floridablanca, Santander, Colombia

    Nelson J. Castellanos

  2. Escuela de Química, Centro de Investigación en Catálisis-CICAT, Universidad Industrial de Santander, Km 2 vía El Refugio, Piedecuesta, Santander, Colombia

    Nelson J. Castellanos & Fernando Martínez

  3. Laboratory of Separation Sciences, Department of Organic Chemistry, University of Ghent, Krijgslaan 281 (S-4), 9000, Ghent, Belgium

    Frédéric Lynen

  4. Department of Inorganic and Physical Chemistry, Centre for Ordered Materials, Organometallics and Catalysis-COMOC, University of Ghent, Krijgslaan 281 (S-3), 9000, Ghent, Belgium

    Nelson J. Castellanos, Shyam Biswas & Pascal Van Der Voort

  5. Chirosciences UMR CNRS 7313 Institut des Sciences Moléculaires de Marseille (iSm2), Aix-Marseille Université, Campus St Jérôme, 13397, Marseille, France

    Henri Arzoumanian

Authors
  1. Nelson J. Castellanos
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  2. Fernando Martínez
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  3. Frédéric Lynen
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  4. Shyam Biswas
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  5. Pascal Van Der Voort
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  6. Henri Arzoumanian
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Corresponding authors

Correspondence to Nelson J. Castellanos or Henri Arzoumanian.

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Castellanos, N.J., Martínez, F., Lynen, F. et al. Dioxygen activation in photooxidation of diphenylmethane by a dioxomolybdenum(VI) complex anchored covalently onto mesoporous titania. Transition Met Chem 38, 119–127 (2013). https://doi.org/10.1007/s11243-012-9668-2

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