Department of Chemistry, Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
Department of Chemical & Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI, 53706, USA.
Angew Chem Int Ed Engl. 2017 Jun 19;56(26):7470-7474. doi: 10.1002/anie.201702772. Epub 2017 May 8.
The first 16 valence electron bis(NHC)Ni complex 1, [( L)ClSi:→Ni(NHC) ], bearing the acyclic amido-chlorosilylene ( L)ClSi: ( L=N(SiMe )Dipp; Dipp=2,6-Pr C H ) and two NHC ligands (N-heterocyclic carbene=:C[(Pr )NC(Me)] ) was synthesized in high yield and structurally characterized. Compound 1 is capable of facile dihydrogen activation under ambient conditions to give the corresponding HSi-NiH complex 2. Most notably, 1 reacts with catechol borane to afford the unprecedented hydroborylene-coordinated (chloro)(silyl)nickel(II) complex 3, {cat( L)SiNi←:BH(NHC) }, via the cleavage of two B-O bonds and simultaneous formation of two Si-O bonds. The mechanism for the formation of 3 was rationalized by means of DFT calculations, which highlight the powerful synergistic effects of the Si:→Ni moiety in the breaking of incredibly strong B-O bonds.
首 16 个价电子双(NHC)Ni 配合物 1，[(L)ClSi:→Ni(NHC)]，带有非循环酰胺-氯硅亚基 (L)ClSi:（L=N(SiMe )Dipp；Dipp=2,6-Pr C H ）和两个 NHC 配体（N-杂环卡宾=:C[(Pr )NC(Me)]），以高产率合成并进行了结构表征。在环境条件下，化合物 1 能够容易地活化氢气，得到相应的 HSi-NiH 配合物 2。值得注意的是，1 与邻苯二酚硼烷反应，通过两个 B-O 键的断裂和两个 Si-O 键的同时形成，得到了前所未有的氢硼化物配位（氯）（硅）镍(II)配合物 3，{cat(L)SiNi←:BH(NHC)}。3 的形成机制通过 DFT 计算得到了合理化，计算强调了 Si:→Ni 部分在打破难以置信的强 B-O 键方面的强大协同效应。
