The three-coordinate imidos (dtbpe)Ni-NR (dtbpe = (t)Bu2PCH2CH2P(t)Bu-2, R = 2,6-(i)Pr2C6H3, 2,4,6-Me3C6H2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni-N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC=CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C=CPh). In the case of R = 2,6-(i)Pr2C6H3, reductive carbonylation results in formation of the (dtbpe)Ni(CO)(2) along with the N-C coupled product keteneimine PhCH-C-N(2,6- (i)Pr2C6H3). Given the ability of the Ni-N bond to have biradical character as suggested by theoretical analysis, H atom abstraction can also occur in (dtbpe)Ni-N{2,6-(i)Pr2C6H3} when this species is treated with HSn(Bu-n)(3). Likewise, the microscopic reverse reaction-conversion of the Ni(I) anilide (dtbpe)Ni{NH(2,6-(i)Pr2C6H3)} to the imido (dtbpe)Ni-N{2,6-(i)Pr2C6H3}-is promoted when using the radical Mes*O() (Mes* = 2,4,6-(t)Bu3C6H2). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni-N{2,6-(i)Pr2C6H3}, are also reported with small, unsaturated molecules such as diphenylketene, benzylisocyanate, benzaldehyde, and carbon dioxide, including the formation of C-N and N-N bonds by coupling reactions. In addition to NMR spectroscopic data and combustion analysis, we also report structural studies for all the cycloaddition reactions involving the imido (dtbpe)Ni-N{2,6-(i)Pr2C6H3}.