Hydrolysis vs dismutation in diorganostannate salts – Synthesis and structural studies of (hydrated)diorganotin cations and triorganotin alkanesulfonates.

[Display omitted] • The stannate salts are versatile precursors to explore hydrolysis chemistry and dismutation reactions. • Tetra(aqua) diorganotin dications are stabilized as multicomponent molecular crystals. • Structural chemistry reveals the role of alkanesulfonates as both coordinating and non-coordinating ligands. The reactions between diphenyl/di- n -butyltin oxide, dialkyl sulfite, and tetra- n -butylammonium iodide (120 °C, 20 h) proceed via isomerization of the sulfite to sulfonate anion and afford the stannate salts, [ n -Bu 4 N][Ph 2 Sn(OSO 2 Et) 3 ] (1) and [ n -Bu 4 N][ n -Bu 2 Sn(OSO 2 n -Pr) 3 ] (2). The solutions of 1 and 2 in acetonitrile upon exposure to atmospheric conditions resulted in the isolation of multicomponent molecular crystals, [Ph 2 Sn(H 2 O) 4 ][ n -Bu 4 N] 3 [OSO 2 Et] 5 ·3H 2 O (3), [ n -Bu 2 Sn(H 2 O) 4 ][ n -Bu 4 N] 2 [OSO 2 n -Pr] 4 ·H 2 O (4) and [ n -Bu 2 Sn(μ -OH)(H 2 O) 2 ] 2 [ n - Bu 4 N ] 2 [ OSO 2 n - Pr ] 4 (5). In the solid state, the diorganotin cations in 3 – 5 owe their stability to O H---O hydrogen bonds with non-coordinating sulfonate anions. Reactions of the previously reported stannate salt, [ n -Bu 4 N][Ph 2 Sn(OSO 2 Me) 3 ] (6) with N -donor ligands provide a manifestation of phenyl group dismutation to afford new coordination assemblies, [Ph 3 Sn(OSO 2 Me)H 2 O][4,4′-bipy] (7) and [Ph 3 Sn(OSO 2 Me)] (8). X-ray crystallographic studies reveal affinity of the alkanesulfonates to function in both primary and secondary coordination sphere that enables the formation of anionic, cationic, and neutral organotin frameworks. [ABSTRACT FROM AUTHOR]