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Role of intermolecular interactions in oxygen transfer catalyzed by silsesquioxane trisilanolate vanadium(V)
Silvia Lovat1, Miriam Mba, Hendrikus C L Abbenhuis
1Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy.
Abstract:
The polyhedral oligomeric silsesquioxane trisilanolate vanadium(V) complex 1 efficiently catalyzes oxidations at room temperature using cumyl hydroperoxide as the terminal oxidant. Sulfoxidations and N-oxidations have been carried out yielding the corresponding products in good yields. The addition of a Lewis base as a coligand can markedly affect reactivity, stability, and chemo- and stereo-selectivity. A proposal for the intermolecular activation, using Gutmann analysis supported by MP2/TZVP calculations, is presented.
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