This work describes reactions of heteroallenes with diamido-diamine cyclam-based Zr(iv) complexes of the general formula (Bn2Cyclam)ZrX2 (X = O(t)Bu, , O(i)Pr, , SPh, , NH(t)Bu, ) as well as the di-orthometallated species ((C6H4CH2)2Cyclam)Zr, . The reactions of isocyanates or isothiocyanates with , or resulted in the formation of N-bonded ureate or thioureate cyclam complexes upon [2 + 2] cycloaddition of the Zr-Namido bonds of the cyclam to the heteroallene (). DFT calculations showed that κ(2)-N,N'-ureate bonding is favoured over κ(2)-N,O-ureates, which in turn may be formed in reactions with bulky isocyanates as 1-naphthyl isocyanate (NpN[double bond, length as m-dash]C[double bond, length as m-dash]O). The reactions of with N,N'-cyclohexylcarbodiimide (CyN[double bond, length as m-dash]C[double bond, length as m-dash]NCy) and carbon disulfide afforded guanidinate and dithiocarbamate fragments, respectively, appended to one of the nitrogen atoms of the cyclam ligand. These reactions represent a reliable method for the synthesis of asymmetrically N-functionalized cyclams giving rise to C1 symmetry Zr(iv) species by addition of one equivalent of heteroallenes. The reaction of (Bn2Cyclam)Zr(NH(t)Bu)2, , with one equivalent of mesityl isocyanate (MesN[double bond, length as m-dash]C[double bond, length as m-dash]O) also proceeds through insertion, involving one Zr-NH(t)Bu bond. However, it was observed that the reaction of (Bn2Cyclam)Zr(NH(t)Bu)2, , with MesN[double bond, length as m-dash]C[double bond, length as m-dash]O follows a different path if the reaction is carried out at 60 °C. In this case the reaction leads to [2 + 2] addition of the Zr-Ncyclam bond to the isocyanate, with a concomitant occurrence of orthometallation of the one benzyl pending group of the cyclam ring. The reaction of (t)BuN[double bond, length as m-dash]C[double bond, length as m-dash]O with the di-orthometallated complex ((C6H4CH2)2Cyclam)Zr, , also gave a κ(2)-N,N'-ureate fragment, by isocyanate addition to the macrocycle. DFT calculations on these systems were conducted in an attempt to rationalise the reactivity patterns observed.