Disilanes with Pentacoordinate Si Atoms by Carbon Dioxide Insertion into Aminodisilanes: Syntheses, Molecular Structures, and Dynamic Behavior

The insertion of carbon dioxide into the Si–N bonds of aminodisilanes ((RR′N)nMe3–nSi)2 affords carbamoyloxydisilanes ((RR′NC­(O)­O)nMe3–nSi)2. Some of the obtained insertion products feature pentacoordinate silicon atoms in the solid state and in solution, with two carbamoyloxy moieties bridging the Si–Si bond. The aminodisilanes and their insertion products were extensively analyzed, including single-crystal X-ray structure analyses. The temperature dependence of the higher coordination was investigated using variable temperature NMR experiments.将二氧化碳插入氨基二硅烷((RR′N)ₙMe₃₋ₙSi)₂的Si–N键中，可生成氨基甲酰氧基二硅烷((RR′NC(O)O)ₙMe₃₋ₙSi)₂。部分所得插入产物在固态与溶液中均呈现五配位硅原子，且有两个氨基甲酰氧基基团桥连Si–Si键。研究团队对该氨基二硅烷及其插入产物进行了全面分析，其中包含单晶X射线结构分析。通过变温核磁共振（Nuclear Magnetic Resonance, NMR）实验，探究了高配位硅中心的温度依赖特性。