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Intricate Road to Linear Anionic Nickel(I) Hexamethyldisilazanide [Ni(N(SiMe<sub>3</sub>)<sub>2</sub>)<sub>2</sub>]<sup>−</sup>
13
Citations
70
References
2022
Year
In this report, we present intricate pathways for the synthesis of linear nickel(I) silylamide K{m}[Ni(NR<sub>2</sub>)<sub>2</sub>] (NR<sub>2</sub> = -N(SiMe<sub>3</sub>)<sub>2</sub>). This is achieved first via the reduction of nickel(II) trisamide Li(donor)<sub>4</sub>[Ni(NR<sub>2</sub>)<sub>3</sub>] (Li(thf)<sub><i>x</i></sub>[<b>1</b>]) with KC<sub>8</sub> in the presence of 18-crown-6 or crypt.222. In due course, the behavior of Li(donor)<sub>4</sub>[Ni(NR<sub>2</sub>)<sub>3</sub>] 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<sub>2</sub>(NR<sub>2</sub>)<sub>3</sub>] (K(toluene)[<b>5</b>]). Finally, a convenient and reliable synthesis of K{m}[Ni(NR<sub>2</sub>)<sub>2</sub>] by ligand exchange of phosphines in [Ni(NR<sub>2</sub>)(PPh<sub>3</sub>)<sub>2</sub>] with K{m}(NR<sub>2</sub>) is presented. This allows for the comprehensive analysis of its electronic properties which reveals a fluxional behavior in solution with tight anion/cation interactions.
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