Tris(pentafluoroethyl)silanol Derivatives and the Lewis Amphoteric Tris(pentafluoroethyl)silanolate Anion, [Si(C(2)F(5))(3)O](−)

While alkyl‐substituted siloxanes are widely known, virtually nothing is known about perfluoroalkyl siloxanes and their congener species, the silanols and silanolates. We recently reported on the tris(pentafluoroethyl)silanide ion, [Si(C(2)F(5))(3)](−), which features Lewis amphoteric character deriving from the pentafluoroethyl substituents and their strong electron‐withdrawing properties. Transferring this knowledge, we investigated the Lewis amphoteric behavior of the tris(pentafluoroethyl)silanolate, [Si(C(2)F(5))(3)O](−). In order to examine such Lewis amphoteric behavior, we first developed a strategy for the synthesis of the corresponding silanol Si(C(2)F(5))(3)OH, which readily condenses at room temperature to the hexakis(pentafluoroethyl)disiloxane, (C(2)F(5))(3)SiOSi(C(2)F(5))(3). Deprotonation of Si(C(2)F(5))(3)OH employing a sterically demanding phosphazene base allows the characterization of the first example of a dimeric triorganosilanolate: the dianionic hexakis(pentafluoroethyl)disilanolate, [{Si(C(2)F(5))(3)O}(2)](2−), implies Lewis amphoteric character of the monomeric [Si(C(2)F(5))(3)O](−) anion.