Transition-Metal Catalyzed Disilane Metathesis Reaction of Organosilicon Compounds

我们发现，环二硅烷如1，2-二硅环丁烷在钯的催化下发生了硅-硅歧化反应形成二聚体(OrganMetallics，14,2556(1995))。讨论了哪些类型的环二硅烷导致了硅-硅歧化反应，以及一种新的通用的环二硅烷合成方法。在制备1.2-二硅环丁烷方面，我们讨论了1，2-炔基二硅烷在新的锆环丁烷催化下的炔偶联反应。然而，大分子烷氧基作为取代基，干扰了Pd(PPh_3)_4和Pd(CNtBu)_2的Si-Si易位反应，生成了双硅基钯配合物。此外，双硅基钯配合物与活化的乙炔反应生成双硅基化产物，而与CpPdAllyl的反应则导致分子内的sily Heck反应

We found that cyclic disilanes such as 1,2-Disilacyclobutanes underwent palladium-catalyzed Si-Si metathesis to from a dimer (Organometallics, 14,2556(1995)). It was considered which types of cyclic disilanes lead to the Si-Si metathesis reaction as well as a new versatile snthetic method of cyclic disilanes. For the preparation of 1.2-disilacyclobutane, new zirconocene promoted alkyne-coupling reaction of 1,2-alkynyldisilane have been discolsed. However bulky alkoxy groups as erminal substituents of alkynes, which is essential for the zirconocene cpoupling reaction, disturbed the Si-Si metathesis reaction with Pd(PPh3)4 and Pd(CNtBu)2 to afford bissilylpalladium complexes respectively. Furthermore, bissilylpalladium complex react with activated acetylene to give bissilylation products, while the reaction with CpPdAllyl led to the intramolecular sily Heck reaction