The Instability of Ni{N(SiMe
<sub>3</sub>
)
<sub>2</sub>
}
<sub>2</sub>
: A Fifty Year Old Transition Metal Silylamide Mystery
作者:Michelle Faust、Aimee M. Bryan、Akseli Mansikkamäki、Petra Vasko、Marilyn M. Olmstead、Heikki M. Tuononen、Fernande Grandjean、Gary J. Long、Philip P. Power
DOI:10.1002/anie.201505518
日期:2015.10.26
the unstable NiII bis(silylamide) NiN(SiMe3)2}2 (1), its THF complex NiN(SiMe3)2}2(THF) (2), and the stable bis(pyridine) derivative trans‐NiN(SiMe3)2}2(py)2 (3), is described. Both 1 and 2 decompose at ca. 25 °C to a tetrameric NiI species, [NiN(SiMe3)2}]4 (4), also obtainable from LiN(SiMe3)2 and NiCl2(DME). Experimental and computational data indicate that the instability of 1 is likely due to
不稳定的Ni II双(甲硅烷基酰胺)Ni N(SiMe 3)2 } 2(1),其THF配合物Ni N(SiMe 3)2 } 2(THF)(2)和稳定的bis(描述了吡啶)衍生物反式Ni N(SiMe 3)2 } 2(py)2(3)。既1和2分解在约 25°C至四聚Ni I物种[[Ni N(SiMe 3)2 }] 4(4),也可从LiN(SiMe 3)2和NiCl 2(DME)获得。实验和计算数据表明1的不稳定性很可能是由于Ni II容易还原为Ni I以及通过分散力使4稳定所致。