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

• Published in: Transition metal chemistry (Weinheim) 2013-03, Vol.38 (2), p.119-127
• Main Authors: Castellanos, Nelson J., Martínez, Fernando, Lynen, Frédéric, Biswas, Shyam, Van Der Voort, Pascal, Arzoumanian, Henri
• Format: Article
• Language: English
• Subjects: Catalysis; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Organometallic Chemistry; Physical Chemistry
• ISSN: 0340-4285; 1572-901X
• DOI: 10.1007/s11243-012-9668-2

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 (O 2 ) 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/TiO 2 /O 2 /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.