Reaction of the highly crowded organotin iodide with AgBF4 gives the fluoride Reaction with AgOSO2C6H4Me followed by workup in moist air gives the hydroxide 2f. With AgOSO2CF3 the product is the organosilicon trifluoromethanesulfonate 5, formed apparently by an unprecedented 1,3-migration of a methyl group from silicon to tin within a cation. Compound 5 and Ph3SiOSO2CF3 are the first silicon trifluoromethanesulfonates to be characterized by X-ray structure determinations. In both the Si−O bonds are long, ca. 1.75 A, consistent with the ready nucleophilic displacement of [OSO2CF3]- from silicon centers. The crystal structures of the fluoride and the hydroxide 2f have also been determined.