No abstract

At low temperatures, the mononuclear copper(I) complex of the tetradentate tripodal aliphatic amine Me(6)tren (Me(6)tren = tris(2-dimethylaminoethyl)amine) [Cu(I)(Me(6)tren)(RCN)](+) first reversibly binds dioxygen to form a 1:1 Cu-O(2) species which further reacts reversibly with a second [Cu(I)(Me(6)tren)(RCN)](+) ion to form the dinuclear 2:1 Cu(2)O(2) adduct. The reaction can be observed using low temperature stopped-flow techniques. The copper superoxo complex as well as the peroxo complex were characterized by resonance Raman spectroscopy. The spectral characteristics and full kinetic and thermodynamic results for the reaction of [Cu(I)(Me(6)tren)(RCN)](+) with dioxygen are reported.

Low temperature stopped-flow methods together with diode array instrumentation have become extremely useful for studying reactions that are too fast at ambient temperatures and/or for detecting reactive intermediates that can only be observed at low temperatures. Furthermore, global analysis fitting methods are described that allow the analysis of complex reaction mechanisms. To illustrate the method the reaction of dioxygen with the tripodal copper() complex [Cu(Me 2 -uns-penp)(CH 3 CN)]ClO 4 (Me 2 -uns-penp = (2-dimethylaminoethyl)bis(2-pyridylmethyl)amine) is discussed as an example.

No abstract

No abstract