The insertion of isocyanates in (Bn(2)Cyclam)ZrX(2) is regioselective; (Bn(2)Cyclam)Zr(OR)(2) produces urea-like moieties by the insertion of RN═C═O in the Zr-N(amido) bonds of the cyclam ring. Depending on the bulkiness of the isocyanate R groups, O- and N-bound ureates are formed. (Bn(2)Cyclam)Zr(NH(t)Bu)(2) reacts with MesN═C═O at the terminal Zr-N bonds.