title: Catalytic catechol oxidation by copper complexes: development of a structure-activity relationship.
abstract: A large library of Cu(II) complexes with mononucleating and dinucleating ligands was synthesized to investigate their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC). X-ray structure determination for a number of these complexes revealed relatively large Cu···Cu distances and the formation of polymeric species. Comparison of the 3,5-DTBC oxidation rates showed that ligands that stabilize the biomimetic dinuclear Cu(II) μ-thiolate complex also result in copper compounds that are much more active in the oxidation of 3,5-DTBC. This oxidation activity is however inhibited by the presence of chloride ions. The highest kcat that was observed was 6900 h(-1), which is one of the highest turnover frequencies reported so far for catechol oxidation in CH3CN.
authors: Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. bouwman@chem.leidenuniv.nl.
authors: Erica C M
authors: EC
authors: Ording-Wenker
authors: Maxime A
authors: MA
authors: Siegler
authors: Martin
authors: M
authors: Lutz
authors: Elisabeth
authors: E
authors: Bouwman
mesh_terms: D002384:Catalysis; D002396:Catechols / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D002396:Catechols; D056831:Coordination Complexes; D008024:Ligands; C054068:3,5-di-tert-butylcatechol; D003300:Copper