Several vanadium(V) dipicolinato complexes were identified as promising candidates for the decomposition of hydroperoxides to corresponding ketones and water. As hydroperoxide decomposition is currently the main industrial route to cyclohexanone, but also inevitably forms the corresponding alcohol, we set out to explain the formation of ketone in a radical-free mechanism that has so far not been reported. The insight gained will be of interest for development of ketone-selective decomposition catalysts. This paper will focus on the computational investigation of different possible mechanisms and the identification of an intramolecular hydrogen transfer to the vanadium catalyst that is key to the observed reactivity.

Computational study of the vanadium-catalyzed decomposition of alkyl hydroperoxides to ketones

253rd National Meeting (2017)

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