Heteroleptic zinc(i) complexes Cp*Zn–ZnL1/2 were synthesized and reactions of Cp*Zn–ZnL22 with t-BuNCO and organoazides RN3 proceeded with insertion into the Zn–Zn bond and formation of novel zinc carbamate, bis-hexazene, triazenide, and azide complexes 4–7.