Silylated Sulfuric Acid: Preparation of a Tris(trimethylsilyl)oxosulfonium [(Me3 Si-O)3 SO]+ Salt.

The chemistry of silylated sulfuric acid, O2 S(OSiMe3 )2 (T2 SO4 , T=Me3 Si; also known as bis(trimethylsilyl) sulfate), has been studied in detail with the aim of synthesizing the formal autosilylation products of silylated sulfuric acid, [T3 SO4 ]+ and [TSO4 ]- , in analogy to the known protonated species, [H3 SO4 ]+ and [HSO4 ]- . The synthesis of the [TSO4 ]- ion only succeeds when a base, such as OPMe3 that forms a weakly coordinating cation upon silylation, is reacted with T2 SO4 , resulting in the formation of [Me3 POT]+ [TSO4 ]- . [T3 SO4 ]+ salts could be isolated starting from T2 SO4 in the reaction with [T-H-T]+ [B(C6 F5 )4 ]- or T+ [CHB11 Br6 H5 ]- when a weakly coordinating anion is used as counterion. All silylated compounds could be crystallized and structurally characterized.