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

The synthesis of new stannates, [Et 3NMe] 2[R 2Sn(OSO 2Me) 4] [R = Me (1), Et (2), Ph (3)] and [Et 3NMe][Ph 3Sn(OSO 2Me) 2] (4) has been achieved from a one pot reaction between R 2SnO (R = Me, Et, Ph) or (Ph 3Sn) 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 [Ph 2Sn(OMe)OS(O)OMe] n (5) and (Ph 3SnO) 2SO (6), respectively. Structural aspects of 1-4 have been elucidated by X-ray crystallography.