Reaction of Dilithio Reagents with PhSiH3: Formation of Siloles and 3‑Silacyclopentenes

The reaction chemistry between 1,4-dilithio-1,3-butadienes (dilithio reagents for short) and PhSiH3 has been investigated. Direct substitution of two hydride ions from PhSiH3 with the dilithio reagents led to multisubstituted siloles (silacyclopentadienes) in diethyl ether solution, with the concomitant generation of LiH. When THF was used as the solvent, the reaction between PhSiH3 and 1,4-bis­(silyl) dilithio reagents afforded cis-3-silacyclopentenes stereoselectively. Experimental results demonstrated that reactive LiH was generated in situ in the reaction system. Formal syn addition of LiH to silacyclopentadiene intermediates would afford silacyclopentenes, most likely via pentavalent organosilicates.