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Copper(I) complexes of the tripodal, tetradentate, aliphatic ligands Me3tren (Me3tren = tris-(2-methylaminoethyl)amine), Isoprop3tren (Isoprop3tren = tris-(2-isopropylaminoethyl)amine) and Me3isoprop3tren (Me3isoprop3tren = tris-(2-isopropylmethylaminoethyl)amine) of the Tren-family (Tren = tris(2-aminoethyl)amine) were prepared and structurally characterized. Furthermore, they were reacted in solution at low temperatures with dioxygen. All complexes formed a short-lived superoxido intermediate complex that could be observed using low temperature stopped-flow techniques prior to consecutive reactions. However, the superoxido complexes were too reactive to allow isolation and full characterization in contrast to previous work.