氧化三配位 Ni(I)硅基配合物时，阻止了 1,2-氢从硅向镍的迁移。
Arrested 1,2-hydrogen migration from silicon to nickel upon oxidation of a three-coordinate Ni(I) silyl complex.
机构信息
Gordon Center for Integrative Science, Department of Chemistry, University of Chicago, Chicago, Illinois 60637, USA.
出版信息
J Am Chem Soc. 2010 Sep 1;132(34):11890-2. doi: 10.1021/ja1052329.
Reaction of the dimeric Ni(I) chloride complex (dtbpe)NiCl (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 = CF(3)SO(3)) with the nickel(0) complex (dtbpe)Ni(mu-C(6)H(6)) (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)][BAr(F)(4)] (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(CH(2)CMe(3))][BAr(F)(4)] (6) with elimination of neopentane.
二聚镍（I）氯化物配合物(dtbpe)NiCl（1）与二甲基硅基钾反应得到三配位镍（I）硅配合物(dtbpe)Ni(SiHMes(2))（2）。或者，2 可以通过 Mes(2)Si(H)OTf（Tf = CF(3)SO(3)）与镍(0)配合物(dtbpe)Ni(mu-C(6)H(6))（3）的氧化加成反应来制备，同时形成易于分离的副产物(dtbpe)Ni(OTf)（4）。2 通过 ferrocenium 的单电子氧化得到反磁性[(dtbpe)Ni(mu-H)SiMes(2)][BAr(F)(4)]（5），这是一个由镍（II）组成的配合物，通过硅到镍的部分 1,2-H 迁移形成，具有不寻常的 3 中心、2 电子键合模式，涉及 Ni、Si 和桥接 H。复合物 5 还可以通过新戊基配合物盐[(dtbpe)Ni(CH(2)CMe(3))][BAr(F)(4)]（6）与 Mes(2)SiH(2)的活化来获得，同时消除新戊烷。
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