The Influence of Weakly Coordinating Cations on the O−H⋅⋅⋅O(−) Hydrogen Bond of Silanol‐Silanolate Anions

The reaction of a saline phosphazenium hydroxide hydrate with siloxanes led to a novel kind of silanol‐silanolate anions. The weakly coordinating behavior of the cation renders the formation of silanol‐silanolate hydrogen bonds possible, which otherwise suffer from detrimental silanolate–oxygen cation interactions. We investigated the influence of various weakly coordinating cations on silanol‐silanolate motifs, particularly with regard to different cation sizes. While large cations favor the formation of intramolecular hydrogen bonds resulting in cyclic structures, the less bulky tetramethyl ammonium cation encourages the formation of polyanionic silanol‐silanolate chains in the solid state.