Litcius/Paper detail

A Copper Cage‐Complex as Mimic of the pMMO Cu<sub>C</sub> Site

Sarah C. Bete, Leander K. May, Philipp Woite, Michael Roemelt, Matthias Otte

2022Angewandte Chemie International Edition29 citationsDOIOpen Access PDF

Abstract

site emerged as a potential active site, but to date it lacks any study on biomimetic resemblance of the coordination environment provided by the enzyme. Here, the synthesis of a cage ligand providing such an environment is reported. Copper is incorporated, and coordination occurs by the two imidazole and one carboxylate group offered by the ligand. Depending on the oxidation state, it can adopt different coordination modes, as evidenced by the solid-state structures and computational investigation. The copper(I) state readily reacts with dioxygen and thereby undergoes CH activation. Moreover, the catalytic aerobic oxidation of hydroquinones as ubiquinol mimics is shown. Clean one-electron oxidation occurs under mild conditions and EPR analysis of the copper(II) state in the presence of water reveals striking similarities to the data obtained from pMMO.

Topics & Concepts

ChemistryMethane monooxygenaseActive siteLigand (biochemistry)CopperCarboxylateImidazolePhotochemistryElectron paramagnetic resonanceCatalysisCombinatorial chemistryStereochemistryOrganic chemistryBiochemistryPhysicsNuclear magnetic resonanceReceptorMetal-Catalyzed Oxygenation MechanismsMicrobial metabolism and enzyme functionPorphyrin and Phthalocyanine Chemistry