Synthesis of Silolide Dianions via Reduction of Dichlorosiloles: Important Role of the Solvent

Abstract

The reduction of 1,1‐dichloro‐2,5‐bistrimethylsilyl‐3,4‐diphenylsilole to silolide dianion by alkali metals was investigated. As previously demonstrated, the outcome of the reaction depends strongly on the applied alkali metal, solvent, reaction conditions, and substituent pattern. We showed that lithium is a powerful reducing agent in THF or DME solvents, the reaction is even faster than the same reaction with sodium. The X‐ray structures of the corresponding dilithio and disodium silolide dianion were investigated, interestingly recrystallization of the dilithio salt results in a coordination polymer. In order to support the synthetic work DFT calculations were performed.

Lithium Salt of 2,5-Bis(trimethylsilyl)stannolyl Anion: Synthesis, Structure, and Nonaromatic Character

“…The aromaticity of alkali metal salts of metallolyl anions and dianions is also an important topic in this field. The family of group 14 metallole dianions (silole [23][24][25][26], germole [26][27][28], stannole [29][30][31], and plumbole [32,33]) has been concluded to be aromatic (III). In contrast, the situation is more complicated in metallolyl monoanions.…”