The bulky 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand provides an excellent platform for a number of reactive nickel multiply-bonded complexes such as nickel carbenes, phosphinidenes, and imidos. To complement the d⁸ Ni(II) imido complex (dtbpe)Ni=N(2,6-di-isopropylphenyl), which exhibits fascinating reactivity, we have prepared via two independent routes the d⁷ complex cations [(dtbpe)Ni=NR]⁺ (R = adamantyl and 2,6-di-isopropylphenyl). The first route involves 1-electron oxidation of the neutral Ni(II) imido by ferrocenium to give the Ni(III) complex cations. The second route involves two-electron oxidation of the Ni(I) triflate (dtbpe)Ni(OTf) by organoazides to give dinitrogen and [(dtbpe)Ni=NR]⁺.