Alkali Metal Di‐tert‐butylphenylsilanides — tBu2PhSiM (M = Li, Na, K) — Syntheses, Structures, and Reactivity

Abstract The alkali metal silanides tBu2PhSiM (M = Li, Na, K) are quantitatively accessible from the reaction of tBu2PhSiBr with alkali metals in heptane, tetrahydrofuran, and benzene at moderately elevated temperature. In contrast to the polymer structure of unsolvated tBu2PhSiNa, the solvated di‐tert‐butylphenylsilanides tBu2PhSiNa(THF), tBu2PhSiK(C6H6), tBu2PhSiK(THF), and tBu2PhSiK(THF)2 possess a novel feature in their crystal structures with a dimeric arrangement of tBu2PhSiM units via π interaction between the tBu2PhSi group and the alkali metal centers. The alkali metal siloxides tBu2PhSiOM (M = Li, Na, K) can be synthesized almost quantitatively from tBu2PhSiM (M = Li, Na, K) with N2O in tetrahydrofuran at —78 °C. Single crystals of the silanol tBu2PhSiOH have been obtained from the protolysis of tBu2PhSiONa with (NH4)2SO4.