Department of Chemistry, Columbia University , New York, New York 10027, United States.
J Am Chem Soc. 2017 Sep 27;139(38):13264-13267. doi: 10.1021/jacs.7b06719. Epub 2017 Sep 13.
The tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl)]methyl ligand, [Tism], has been employed to form the magnesium carbatrane compound, [Tism]MgH, which possesses a terminal hydride ligand. Specifically, [Tism]MgH is obtained via the reaction of [Tism]MgMe with PhSiH. The reactivity of [Tism]MgMe and [Tism]MgH allows access to a variety of other structurally characterized carbatrane derivatives, including [Tism]MgX [X = F, Cl, Br, I, SH, N(H)Ph, CH(Me)Ph, OCMe, SCMe]. In addition, [Tism]MgH is a catalyst for (i) hydrosilylation and hydroboration of styrene to afford the Markovnikov products, Ph(Me)C(H)SiHPh and Ph(Me)C(H)Bpin, and (ii) hydroboration of carbodiimides and pyridine to form N-boryl formamidines and N-boryl 1,4- and 1,2-dihydropyridines, respectively.
三[（1-异丙基苯并咪唑-2-基）二甲基硅基]甲基配体[Tism]用于形成镁卡巴他烯化合物[Tism]MgH，其具有末端氢化物配体。具体而言，[Tism]MgH 通过[Tism]MgMe 与 PhSiH 的反应获得。[Tism]MgMe 和 [Tism]MgH 的反应性允许获得各种其他结构表征的卡巴他烯衍生物，包括[Tism]MgX [X = F、Cl、Br、I、SH、N(H)Ph、CH(Me)Ph、OCMe、SCMe]。此外，[Tism]MgH 是（i）苯乙烯的硅氢化和硼氢化反应的催化剂，生成 Markovnikov 产物 Ph(Me)C(H)SiHPh 和 Ph(Me)C(H)Bpin，以及（ii）碳二亚胺和吡啶的硼氢化反应，分别生成 N-硼基甲脒和 N-硼基 1,4-和 1,2-二氢吡啶。
