Role of Intermolecular Interactions in Oxygen Transfer Catalyzed by Silsesquioxane Trisilanolate Vanadium(V)

被引：28
作者：
Lovat, Silvia [1 ]
Mba, Miriam [1 ]
Abbenhuis, Hendrikus C. L. [2 ]
Vogt, Dieter [2 ]
Zonta, Cristiano [1 ]
Licini, Giulia [1 ]
机构：
[1] Univ Padua, Dept Chem Sci, I-35131 Padua, Italy
[2] Eindhoven Univ Technol, Inst Catalysis, Lab Homogeneous Catalysis, NL-5600 MB Eindhoven, Netherlands
来源：
INORGANIC CHEMISTRY | 2009年 / 48卷 / 11期
关键词：
LEWIS-BASE ACTIVATION; ENANTIOSELECTIVE ADDITION; ORGANOMETALLIC REAGENTS; KINETIC RESOLUTION; FUNCTIONAL MODELS; HYDROGEN-PEROXIDE; HYDROXAMIC ACIDS; ALLYLIC ALCOHOLS; SECONDARY-AMINES; OXIDATION;
D O I：
10.1021/ic802191z
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
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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页码：4724 / 4728
页数：5
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