Institut für Anorganische Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany.
Chemistry. 2011 Mar 1;17(10):2931-8. doi: 10.1002/chem.201002890. Epub 2011 Feb 2.
By employing the 2,2'-thiobis(2,4-di-tert-butylphenolate) ligand ((S)L(2-)) a novel oxovanadium(V) complex, (PPh(4))(2)[(S)LV(O)(μ(2)-O)(2)V(O)(S)L] (1), was synthesised that exhibits haloperoxidase activity: on addition of H(2)O(2) a sequence of successive peroxide formation and intramolecular thioether oxidation events (sulfoxide and sulfone) led to a mixture of five products, which were all identified unambiguously, partly through an independent synthesis and characterisation. It was shown that internal thioether oxidation proceeds through peroxide formation, but the sulfoxidation of external thioether functions requires further activation of the peroxide function by protons or alkyl cations. Consistently, the employment of tBuOOH instead of H(2)O(2) led to a very active system for the catalytic sulfoxidation of thioethers.
采用 2,2'-硫代双(2,4-二叔丁基苯酚)配体((S)L(2-))，合成了一种新型的氧钒(V)配合物[(PPh(4))(2)(S)LV(O)(μ(2)-O)(2)V(O)(S)L，该配合物具有过氧化物酶活性：在加入 H(2)O(2)后，一系列连续的过氧化物形成和分子内硫醚氧化事件（亚砜和砜）导致生成了五种产物的混合物，通过独立的合成和表征，这些产物均被明确地鉴定出来。结果表明，内部硫醚氧化通过过氧化物形成进行，但外部硫醚的氧化功能需要通过质子或烷基阳离子进一步激活过氧化物功能。一致地，采用 tBuOOH 而不是 H(2)O(2)代替 H(2)O(2)导致了一种非常活跃的体系，可用于催化硫醚的氧化。
