The synthesis, X-ray structure, and NMR (H-1, C-13, O-17) and magnetic char
acterization of the complexes [Co(CO)(2)(tmpo)] (1) and [Co4O(OOCNC9H18)(6)
] (2) are reported. Reaction of Co-2(CO)(8) in the presence of a 4-fold exc
ess of tmpo yields in a few minutes the blue carbamato complex 2 in >80% yi
eld. The reaction possibly takes place by, a cascade mechanism with the com
plex [Co(CO)(2)tmpol] (I) as an intermediate and the nitroxyl radical actin
g as an oxidizing agent.