The reaction of tin(IV) iodide with phosphines: formation of new halotin anions

The reaction of SnI4 with each of a primary, secondary and tertiary phosphine has been investigated and in none of the cases are simple adducts formed. With Cy3P, [Cy3PI](+) salts of both [SnI3](-) (1) and [SnI5](-) (2) are isolated arising from reactions involving both reduction at tin and halogen transfer. With the secondary and primary amines Ph2PH and CyPH2, respectively, additional HI elimination reactions occur and the salts [Ph2PH2](+)(6)[Sn3I12](6-) (3), [Ph2PH2](+)(2)[SnI6](2-) (4) and [CyPH3](+)(2)[SnI4](2-) (5) have been isolated. Compounds 1-5 have been characterised crystallographically.