You Qing, Zhang Jie, Zhou Xigeng
Department of Chemistry, Shanghai Key Laboratory of, Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
Chemistry. 2020 Jun 18;26(34):7702-7710. doi: 10.1002/chem.202001207. Epub 2020 May 26.
A new method for the modification of a silylamino ligand has been developed through mono and dual C(sp )-H/Si-H cross-dehydrocoupling with silanes. The reaction of [LY{η -(C,N)-CH Si(Me )NSiMe }] (L=bis(2,6-diisopropylphenyl)-β-diketiminato, L' (1 '); L=tris(3,5-dimethylpyrazolyl)borate, Tp (1 )) with 2 equivalents of PhSiH in toluene gave the complexes [LY{η -(C,N)-C(SiH Ph) Si(Me )NSiMe }] (L=L' (2 ); L=Tp (2 )). Moreover, 1 reacted with the secondary silanes Ph SiH and Et SiH to afford the corresponding mono C-H activation products [Tp Y{η -(C,N)-CH(SiHR )Si(Me )NSiMe }] (R=Ph (4 b); R=Et (4 c)). The equimolar reaction of 1 with PhSiH also produced the mono C-H activation product 4 a ([Tp Y{η -(C,N)-CH(SiH Ph)Si(Me )NSiMe }(thf)]). A study of their reactivity showed that4 a facilely reacted with 2 equivalents of benzothiazole by an unusual 1,1-addition of the C=N bond of the benzothiazolyl unit to the Si-H bond to give the C-H/Si-H cross-dehydrocoupling product [(Tp )Y{η -(N,N,N)-N(SiMe )SiMe CH Si(Ph)(CSC H N)(CHSC H N)}] (5). These results indicate that this modification endows the silylamino ligand with novel reactivity.
通过与硅烷进行单和双C(sp³)-H/Si-H交叉脱氢偶联反应，开发了一种修饰硅氨基配体的新方法。[LY{η⁵-(C,N)-CH₂Si(Me)₂NSiMe₂}]（L=双(2,6-二异丙基苯基)-β-二酮亚胺基，L' (1')；L=三(3,5-二甲基吡唑基)硼酸盐，Tp (1)）与2当量的PhSiH在甲苯中反应，得到配合物[LY{η⁵-(C,N)-C(SiH₂Ph)Si(Me)₂NSiMe₂}]（L=L' (2)；L=Tp (2)）。此外，1与仲硅烷Ph₂SiH和Et₂SiH反应，得到相应的单C-H活化产物[TpY{η⁵-(C,N)-CH(SiHR₂)Si(Me)₂NSiMe₂}]（R=Ph (4b)；R=Et (4c)）。1与PhSiH的等摩尔反应也产生了单C-H活化产物4a（[TpY{η⁵-(C,N)-CH(SiH₂Ph)Si(Me)₂NSiMe₂}(thf)]）。对它们反应活性的研究表明，4a通过苯并噻唑基单元的C=N键与Si-H键进行不寻常的1,1-加成，与2当量的苯并噻唑容易反应，得到C-H/Si-H交叉脱氢偶联产物[(Tp)Y{η⁵-(N,N,N)-N(SiMe₂)SiMe₂CH₂Si(Ph)(CSC₆H₄N)(CHSC₆H₄N)}] (5)。这些结果表明，这种修饰赋予了硅氨基配体新的反应活性。
