TY  - JOUR
A1  - Guelzow, Jana
A1  - Hoerner, Gerald
A1  - Strauch, Peter
A1  - Stritt, Anika
A1  - Irran, Elisabeth
A1  - Grohmann, Andreas
T1  - Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity
JF  - Chemistry - a European journal
N2  - Deprotonation of ligand-appended alkoxyl groups in mononuclear copper(II) complexes of N,O ligands L-1 and L-2, gave dinuclear complexes sharing symmetrical Cu2O2 cores. Molecular structures of these mono-and binuclear complexes have been characterized by XRD, and their electronic structures by UV/Vis, H-1 NMR, EPR and DFT; moreover, catalytic performance as models of catechol oxidase was studied. The binuclear complexes with anti-ferromagnetically coupled copper(II) centers are moderately active in quinone formation from 3,5-di-tert-butyl-catechol under the estab-lished conditions of oxygen saturation, but are strongly activated when additional dioxygen is administered during catalytic turnover. This unforeseen and unprecedented effect is attributed to increased maximum reaction rates v(max), whereas the substrate affinity KM remains unaffected. Oxygen administration is capable of (partially) removing limitations to turnover caused by product inhibition. Because product inhibition is generally accepted to be a major limitation of catechol oxidase models, we think that our observations will be applicable more widely.
Y1  - 2017
U6  - https://doi.org/10.1002/chem.201605868
SN  - 0947-6539
SN  - 1521-3765
VL  - 23
SP  - 7009
EP  - 7023
PB  - Wiley-VCH
CY  - Weinheim
ER  -