η²-Organoazide Complexes of Nickel and Their Conversion to Terminal Imido Complexes via Dinitrogen Extrusion

1-Adamantyl- and mesitylazide react with [(dtbpe)Ni]2(eta2-mu-C6H6) to give the eta2 organic azide adducts (dtbpe)Ni(eta2-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)NiNR (R = Ad, 4a; Mes, 4b), undergoing intramolecular loss of dinitrogen upon mild thermolysis.