Intricate Road to Linear Anionic Nickel(I) Hexamethyldisilazanide [Ni(N(SiMe))].

In this report, we present intricate pathways for the synthesis of linear nickel(I) silylamide K{m}[Ni(NR)] (NR = -N(SiMe)). This is achieved first via the reduction of nickel(II) trisamide Li(donor)[Ni(NR)] (Li(thf)[]) with KC in the presence of 18-crown-6 or crypt.222. In due course, the behavior of Li(donor)[Ni(NR)] as a source of masked two-coordinate nickel(II) hexamethyldisilazanide is explored, leading to the formation of nickel(I) and nickel(II) N-donor adducts, as well as metal-metal-bonded dinickel(I) trisamide K(toluene)[Ni(NR)] (K(toluene)[]). Finally, a convenient and reliable synthesis of K{m}[Ni(NR)] by ligand exchange of phosphines in [Ni(NR)(PPh)] with K{m}(NR) is presented. This allows for the comprehensive analysis of its electronic properties which reveals a fluxional behavior in solution with tight anion/cation interactions.