Novel Si(II)+ and Ge(II)+ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction†,Organic Process Research & Development

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Novel Si(II)+ and Ge(II)+ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction†
Organic Process Research & Development ( IF 3.1 ) Pub Date : 2020-08-10 , DOI: 10.1021/acs.oprd.0c00214
Elke Fritz-Langhals ₁ , Sven Werge ₁ , Sotirios Kneissl ₁ , Phillip Piroutek ₁

Affiliation

Novel catalytically active cationic Si(II) and Ge(II) compounds were synthesized and isolated in pure form. The Ge(II)⁺-based compounds proved to be stable against air and moisture and therefore can be handled very easily. All compounds efficiently catalyze the oxidative coupling of hydrosil(ox)anes with aldehydes and ketones as oxidation reagents and simultaneously the reductive ether coupling at very low amounts of <0.01 mol %. Because the catalysts also catalyze the reversible cyclotrimerization of aldehydes, paraldehyde can be used as a convenient source for acetaldehyde in siloxane coupling. It is shown that the reaction is especially suitable to make siloxane copolymers. Moreover, a new fluorine-free weakly coordinating boronate anion, B(SiCl₃)₄^–, was successfully combined with the Si(II) and Ge(II) cations to give the stable catalytically active ion pairs Cp*Si:⁺B(SiCl₃)₄^–, Cp*Ge:⁺B(SiCl₃)₄^–, and [Cp(SiMe₃)₃Ge:⁺]B(SiCl₃)₄^–.

中文翻译：

在有机硅化学中作为高效催化剂的新型Si（II）⁺和Ge（II）⁺化合物：硅氧烷偶联反应†

合成并分离了具有新型催化活性的阳离子Si（II）和Ge（II）化合物。事实证明，基于Ge（II）⁺的化合物对空气和湿气稳定，因此可以非常容易地处理。所有化合物均有效催化氢化硅（氧）烷与醛和酮作为氧化试剂的氧化偶联，并同时以非常低的<0.01 mol％的量进行还原性醚偶联。因为该催化剂还催化醛的可逆环三聚，所以对苯二酚可用作硅氧烷偶联中乙醛的方便来源。结果表明该反应特别适合于制备硅氧烷共聚物。此外，新的无氟弱配位硼酸阴离子B（SiCl ₃）₄^–，成功地与Si（II）和Ge（II）的阳离子结合以得到稳定的催化活性离子对的Cp *的Si：⁺乙硅烷（SiCl ₃）₄^-中，Cp *戈：⁺乙硅烷（SiCl ₃）₄^-，和[Cp（SiMe ₃）₃ Ge：⁺ ] B（SiCl ₃）₄^–。

更新日期：2020-08-21

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