Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario, L2S 3 A1, Canada.
Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Carrer Maria Aurèlia Capmany 69, 17003, Girona, Spain.
Chemistry. 2022 Dec 15;28(70):e202202799. doi: 10.1002/chem.202202799. Epub 2022 Nov 22.
Reactions of silicon and germanium dichlorides L⋅ECl (E=Si, L=IPr; E=Ge, L=dioxane) with the phosphinoamidinato-supported disilylene ({κ (N,P)-NNP}Si) resulted in formal tetrylene insertions into the Si-Si bond. In the case of the reaction with silylene, two products were isolated. The first product ({κ (N,P)-NNP}Si) SiCl , is the formal product of direct SiCl insertion into the Si-Si bond of ({κ (N,P)-NNP}Si) and thus features two separated silylamido silylene centers. Over time, migration of the SiCl group to a lateral position afforded the second product, the disilylene {κ (Si,P)-SiCl NNP}Si-Si{κ (N,P)-NNP}. In contrast, insertion of GeCl resulted only in the isolation of the germanium analogue of {κ (Si,P)-SiCl NNP}Si-Si{κ (N,P)-NNP}, containing a Ge atom in the central position namely, compound {κ (Si,P)-SiCl NNP}Ge-Si{κ (N,P)-NNP}, which is a rare example of a silylene-germylene. Finally, reaction of disilylene ({κ (N,P)-NNP}Si) with SiCl and SiHCl led to the formation of the new bis(silyl)silylene, ({NNP}SiCl ) Si:. All four new products from these insertion reactions have been characterized by multinuclear NMR and single-crystal X-ray diffraction studies.
硅和锗二氯化物 L⋅ECl（E=Si，L=IPr；E=Ge，L=二氧六环）与膦酰胺基二硅烯（{κ（N，P）-NNP}Si）反应，导致硅-硅键的正式四聚体插入。在与硅烯的反应中，分离出两种产物。第一种产物{κ（N，P）-NNP}Si） SiCl ，是直接 SiCl 插入{κ（N，P）-NNP}Si 的 Si-Si 键的形式产物，因此具有两个分离的硅亚胺硅烯中心。随着时间的推移，SiCl 基团迁移到侧向位置得到第二种产物，二硅烯{κ（Si，P）-SiCl NNP}Si-Si{κ（N，P）-NNP}。相比之下，GeCl 的插入仅导致{κ（Si，P）-SiCl NNP}Si-Si{κ（N，P）-NNP}的锗类似物的分离，其中中心位置含有一个 Ge 原子，即化合物{κ（Si，P）-SiCl NNP}Ge-Si{κ（N，P）-NNP}，这是一个罕见的硅烯-锗烯例子。最后，二硅烯{κ（N，P）-NNP}Si）与 SiCl 和 SiHCl 的反应导致了新的双（硅基）硅烯的形成，（{NNP}SiCl ） Si：。这些插入反应的所有四个新产物都通过多核 NMR 和单晶 X 射线衍射研究进行了表征。
