Synthesis and characterization of di-/triorgano stannates bearing tin-sulfonate bonds

The synthesis of new stannates, [Et3NMe]2[R2Sn(OSO2Me)4] [R = Me (1), Et (2), Ph (3)] and [Et3NMe][Ph3Sn(OSO2Me)2] (4) has been achieved from a one pot reaction between R2SnO (R = Me, Et, Ph) or (Ph3Sn)2O and dimethylsulfite [(MeO)2S = O] in the presence of triethylamine. An important step in this synthetic protocol involves a sulfur-centered Arbuzov-type rearrangement in dimethylsulfite and in situ formation of the methanesulfonate moiety. On the contrary, direct reaction of diphenyl/triphenyltin oxide and dimethylsulfite proceeds without such rearrangement and affords [Ph2Sn(OMe)OS(O)OMe]n (5) and (Ph3SnO)2SO (6), respectively. Structural aspects of 1–4 have been elucidated by X-ray crystallography.