Coordination Chemistry of Cyclic Disilylated Germylenes and Stannylenes with Group 11 Metals
摘要:
Reactions of Et3P adducts of bissilylated germylenes and stannylenes with gold, silver, and copper cyanides led to cyanogermyl or -stannyl complexes of the respective metals. In the course of the reaction the phosphine moved to the metal, while the cyanide migrated to the low-coordinate group 14 element. The respective gold complexes were found to be monomeric, whereas the silver and copper complexes exhibited a tendency to dimerize in the solid state. Attempts to abstract the phosphine ligand with B(C6F5)(3) led only to the formation of adducts with the borane coordinating to the cyanide nitrogen atom.
The reactions of two cyclic germylene phosphane adducts with monosubstituted acetylenes caused the formation of spirocyclic germanes, which is postulated to occur by double acetylene insertion into germylene attached bonds. Further insertion of the formed cyclic divinylgermylene into transannular Si–Si or Si–Ge bonds provides the spirocyclic germanes. Thermal treatment of two germacyclopropenes, formed