1-Adamantyl- and mesitylazide react with [(dtbpe)Ni](2)(eta(2)-mu-C6H6) to give the eta(2) organic azide adducts (dtbpe)Ni(eta(2)-N3R) (R = Ad, 3a; Mes, 3b) that have been isolated in good yields and crystallographically characterized. These azide adducts are intermediates in the formation of the corresponding terminal imido complexes (dtbpe)Ni=NR (R = Ad. 4a; Mes, 4b), undergoing intramolecular loss of dinitrogen upon mild thermolysis.