Daniel H. Friese^§, Christof Hättig^*§, Markus Rohe^‖, Klaus Merz^†, André Rittermeier^⊥, and Martin Muhler^‡
Lehrstuhl für Anorganische Chemie I, Ruhr-Universität Bochum, Universitätsstraße 150, D-44801 Bochum, Germany, Lehrstuhl für Technische Chemie, Ruhr-Universität Bochum, Universitätsstraße 150, D-44801 Bochum, Germany, and Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Universitätsstraße 150, D-44801 Bochum, Germany

J. Phys. Chem. C, 114, 19415-19418 (2010)

Received: 24 July, 2010; Revised Manuscript Received: September 23, 2010

he oxidation of 2-propanol by titanium peroxo complexes is investigated in a combined synthetic, spectroscopic, and computational study. We find in quantum chemical calculations for the thermal reaction in protic solvents that the temporary protonation of the peroxo group activates the latter as electrophile. This transient species is amenable to a concerted transfer of two electrons and a proton from the secondary C atom of 2-propanol. Simultaneously, the carbonyl group is formed and the alcoholic proton is transferred to the solvent. In line with the results of the calculations, we find experimentally that the activity of the titanium peroxo complexes as oxidant depends on the pH value of the reaction medium.

^*To whom correspondence should be addressed: Tel: +49 234 32 28082, Fax: +49 234 32 14045, E-mail:christof.haettig@theochem.rub.de
^†Lehrstuhl für Anorganische Chemie I, Ruhr-Universität Bochum.
^‡Lehrstuhl für Technische Chemie, Ruhr-Universität Bochum.
^§Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum.
^‖Present address: Sachtleben Chemie GmbH, LAB, Dr.-Rudolf-Sachtleben-Str. 4, 47198 Duisburg, Germany.
^⊥Present address: Bayer Technology Services GmbH, BTS-PT-RPT-REC, Leverkusen, E 41, Germany.

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