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Haloperoxidase Activity of Oxovanadium(V) Thiobisphenolates
Author(s) -
Werncke C. Gunnar,
Limberg Christian,
Knispel Christina,
Metzinger Ramona,
Braun Beatrice
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002890
Subject(s) - thioether , sulfoxide , peroxide , sulfone , chemistry , intramolecular force , medicinal chemistry , ligand (biochemistry) , catalysis , alkyl , aryl , polymer chemistry , stereochemistry , organic chemistry , receptor , biochemistry
By employing the 2,2′‐thiobis(2,4‐di‐ tert ‐butylphenolate) ligand ( S L 2− ) a novel oxovanadium(V) complex, (PPh 4 ) 2 [ S L V(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 t BuOOH instead of H 2 O 2 led to a very active system for the catalytic sulfoxidation of thioethers.