Tetra-Amido Macrocyclic Ligand (TAML) at Silicon(IV): A Structurally Constrained, Water-Soluble Silicon Lewis Superacid

Tetracoordinate silicon species are typically tetrahedral, weak Lewis acids, and often sensitive to moisture. In this study, we present a tetra-amido macrocyclic ligand (TAML)-substituted Si(IV), isolated as its bis(pyridine) adduct. Due to structural constraint toward anti van't-Hof/Le Bel geometry, this compound exhibits Lewis superacidity and effectively catalyzes the hydroboration of pyridine. Kinetic and computational analyses of the catalytic cycle reveal that TAML-Si(IV) acts as a hydride transfer agent, and the hydrido silicate key intermediate is isolated. Notably, the Lewis acid is highly soluble (5 g/L) and long-term stable in water. Unlike previously described silicon-H