The First Sideways-Bonded Peroxo Complex for a Tetraaminecobalt(III) Species

Cobalt(II) salts react with H2O2 in the presence of 2 equiv of tetramethylethylenediamine (tmen) to produce a stable sideways bonded mononuclear peroxo complex [Co(tmen)2O2]ClO4 which has been characterized chemically and by a single crystal X-ray determination. This is the first such tetraaminecobalt(III) complex, indeed, the first for any tetraaminemetal ion complex. The mononuclear peroxo complex can also be synthesized by O22- anation of cis-[Co(tmen)2(OH2)2]3+. This reaction is reversed in acid, and this offers the potential to develop Co(III) catalyzed oxidation reactions.