To further understand copper-promoted oxidation reactions, the Cu(I) complexes LCuX (L = N,N'-di-tert-butyl-N,N'-dimethylethylenediamine; X = benzoylformate (BF) or p-nitro-benzoylformate) were synthesized, fully characterized by X-ray crystallography and spectroscopy in solution, and their reactivity with O-2 at -80 degrees C examined. Oxidative decarboxylation of the alpha-ketocarboxylate ligand was observed, but only to a significant extent when cyclohexene, cyclooctene, or acetonitrile was present. Spectroscopic and conductivity data are consistent with mechanistic postulates involving displacement of the alpha-ketocarboxylate by the additives to a small extent, followed by oxygenation of the LCu(I) moiety to yield copper oxygen species that subsequently induce decarboxylation. To test these hypotheses, spectroscopic and kinetic studies of the reactions of Bu4NBF with preformed mu-eta(2);eta(2)-peroxodicopper(II) and/or bis(mu-oxo)dicopper(III) complexes supported by L or N,N,N',N'-tetramethylpropylenediamine were performed. In an illustration of a new mode of reactivity for such dicopper-oxygen cores, decarboxylation of the added alpha-ketocarboxylate was observed and the intermediacy of a carboxylate-bridged mu-eta(2);eta(2)-peroxodicopper(II) complex was implicated.