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