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

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)2CuII 2(O2)]2+ together with [CuI(Me6tren)(DMSO)]+ and [CuII(Me6tren)(OH)]+ in the overall reaction.