Journalartikel

Autorenliste: Chaloner, L; Askari, MS; Kutteh, A; Schindler, S; Ottenwaelder, X

Jahr der Veröffentlichung: 2011

Seiten: 4204-4211

Zeitschrift: European Journal of Inorganic Chemistry

Bandnummer: 2011

Heftnummer: 27

ISSN: 1434-1948

DOI Link: https://doi.org/10.1002/ejic.201100080

Verlag: Wiley-VCH Verlag

Abstract: 
Copper(II)-hydroperoxo species are proposed as key intermediates in the catalytic cycles of copper-monooxygenase enzymes that perform C-H bond hydroxylation. Herein we report on the oxidation chemistry of a copper(II) complex with a coordinating cryptand based on a peralkylated tetradentate tris(2-aminoethyl) amine (tren) moiety. X-ray crystallography of the copper(II) acetate complex of this cryptand revealed that the copper(II) ion is in a square-pyramidal environment, with the cryptand acting only as a tridentate ligand. This geometry is conserved in solution and likely results from restraints imposed by the semi-rigid cryptand. Reaction of this complex with basic hydrogen peroxide in methanol led to the decomposition of the complex with an oxygen-atom transfer to the ligand, as evidenced by mass spectrometry analysis after reaction and demetallation. Low-temperature stopped-flow experiments (down to -90 degrees C) support the formation of a copper(II)-hydroperoxo intermediate, CuOOH, before ligand oxygenation occurs. It is proposed that this intermediate performs the oxygen-atom transfer to a weak benzylic C-H bond of the cryptand, thereby mimicking the behavior of dopamine-beta-hydroxylase.

Harvard-Zitierstil: Chaloner, L., Askari, M., Kutteh, A., Schindler, S. and Ottenwaelder, X. (2011) Formation and Reactivity of a Biomimetic Hydroperoxocopper(II) Cryptate, European Journal of Inorganic Chemistry, 2011(27), pp. 4204-4211. https://doi.org/10.1002/ejic.201100080

APA-Zitierstil: Chaloner, L., Askari, M., Kutteh, A., Schindler, S., & Ottenwaelder, X. (2011). Formation and Reactivity of a Biomimetic Hydroperoxocopper(II) Cryptate. European Journal of Inorganic Chemistry. 2011(27), 4204-4211. https://doi.org/10.1002/ejic.201100080