Unusual Stability of an end-on Superoxido Copper(II) Complex under Ambient Conditions

Chiara Eleonora Campi; Konstantinos Parkatzidis; Athina Anastasaki; Siegfried Schindler

doi:10.1002/chem.202401634

Unusual Stability of an end-on Superoxido Copper(II) Complex under Ambient Conditions

Chemistry. 2024 May 8:e202401634. doi: 10.1002/chem.202401634. Online ahead of print.

Authors

Chiara Eleonora Campi¹, Konstantinos Parkatzidis², Athina Anastasaki², Siegfried Schindler³

Affiliations

¹ Justus Liebig University, Chemistry, GERMANY.
² ETH Zürich, Department of Materials, SWITZERLAND.
³ Justus-Liebig-Universität Gießen, Inorganic Chemistry, Heinrich-Buff-Ring 58, 35392, Gießen, GERMANY.

PMID: 38718317
DOI: 10.1002/chem.202401634

Abstract

Superoxido copper complexes play an important role as usually short-lived intermediates in biology and chemistry. The unusual stability of an end-on superoxido copper complex observed in an oxygen-enhanced atom transfer radical polymerization (ATRP) led to a detailed mechanistic investigation of the formation of [CuII(Me6tren)(O2•-)]+ (Me6tren = tris(2-dimethyl-aminoethyl)amine) under ambient conditions. The persistence of the superoxido copper complex could be explained by a reaction cycle including the peroxido complex [(Me6tren)2CuII2(O2)]2+ together with [CuI(Me6tren)(DMSO)]+ and [CuII(Me6tren)(OH)]+ in the overall reaction.

Keywords: copper; dioxygen activation; mechanism; polymerisation; superoxido complex.