title: Haloperoxidase activity of oxovanadium(V) thiobisphenolates.
abstract: 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.
authors.affiliation: Institut für Anorganische Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany.
authors.forename: C Gunnar
authors.initials: CG
authors.lastname: Werncke
authors.forename: Christian
authors.initials: C
authors.lastname: Limberg
authors.forename: Christina
authors.initials: C
authors.lastname: Knispel
authors.forename: Ramona
authors.initials: R
authors.lastname: Metzinger
authors.forename: Beatrice
authors.initials: B
authors.lastname: Braun