Arrested 1,2-Hydrogen Migration from Silicon to Nickel upon Oxidation of a Three-Coordinate Ni(I) Silyl Complex

作者：Iluc Vlad M; Hillhouse Gregory L^*

来源：Journal of the American Chemical Society, 2010, 132(34): 11890-11892.

DOI：10.1021/ja1052329

Reaction of the dimeric Ni(I) chloride complex [(dtbpe)-NiCl](2) (1) with dimesitylsilyl potassium affords the three-coordinate Ni(I) silyl complex (dtbpe)Ni(SiHMes(2)) (2). Alternatively, 2 can be prepared by an oxidative-addition reaction of Mes(2)Si(H)OTf (Tf = CF3SO3) with the nickel(0) complex [(dtbpe)Ni](2)(mu-C6H6) (3), with (dtbpe)Ni(OTf) (4) formed as an easily separable byproduct. The one-electron oxidation of 2 by ferrocenium affords diamagnetic [(dtbpe)Ni(mu-H)SiMes(2)][BAr4F] (5), a Ni(II) complex formed by partial 1,2-H migration from silicon to nickel and featuring an unusual 3-center, 2-electron bonding motif between Ni, Si, and the bridging H. Complex 5 was also obtained from Mes(2)SiH(2) activation by the neopentyl complex salt [(dtbpe)Ni(CH2CMe3)]-[BAr4F] (6) with elimination of neopentane.

• 出版日期2010-9-1