Reckziegel Alexander, Battistella Beatrice, Schmidt Andreas, Werncke C Gunnar
Department of Chemistry, Philipps University Marburg, Hans-Meerwein Straße 4, D-35037 Marburg, Germany.
Institute of Chemistry, Humboldt-University Berlin, Brook-Taylor-Str. 2, D-12489 Berlin, Germany.
Inorg Chem. 2022 May 23;61(20):7794-7803. doi: 10.1021/acs.inorgchem.2c00214. Epub 2022 May 6.
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.
在本报告中，我们展示了线性镍（I）硅烷基酰胺K{m}[Ni(NR)]（NR = -N(SiMe)）的复杂合成途径。首先通过在18-冠-6或穴醚.222存在下，用KC还原三酰胺镍（II）Li(donor)[Ni(NR)]（Li(thf)[]）来实现。在此过程中，探索了Li(donor)[Ni(NR)]作为掩蔽的二配位镍（II）六甲基二硅氮烷源的行为，导致形成镍（I）和镍（II）的氮供体加合物，以及金属-金属键合的二镍（I）三酰胺K(toluene)[Ni(NR)]（K(toluene)[]）。最后，提出了一种通过[Ni(NR)(PPh)]中的膦与K{m}(NR)进行配体交换来方便可靠地合成K{m}[Ni(NR)]的方法。这使得能够对其电子性质进行全面分析，揭示了在溶液中具有紧密阴离子/阳离子相互作用的动态行为。
