Role of intermolecular interactions in oxygen transfer catalyzed by silsesquioxane trisilanolate vanadium(V).
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.
Lovat
Silvia
S
Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy.
Mba
Miriam
M
Abbenhuis
Hendrikus C L
HC
Vogt
Dieter
D
Zonta
Cristiano
C
Licini
Giulia
G
D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism
D009942:Organometallic Compounds; D010100:Oxygen