Intramolecularly coordinated organotin(IV) sulphides and their reactivity to iodine

Organotin(IV) sulphides (LSnPhS)2 (3) and (LSnPh2)2S (4) containing O,C,O chelating ligand (L = 2,6-(t BuOCH2)2C6H3−) were prepared by the reaction of parent organotin chlorides LSnPhCl2 (1) and LSnPh2Cl (2) with Na2S · 9H2O in toluene/water. Both sulphides were characterized by the help of elemental analysis, ESI-mass spectrometry, 1H, 13C 119Sn NMR spectroscopy and the molecular structure of 3 was determined by X-ray diffraction techniques. Compounds 3 and 4 react with I2 to organotin iodides LSnPhI2 (5) and LSnPh2I (6), instead of intended iodolysis of phenyl groups. Triorganotin iodide 6 reacts with the additional molecule of I2 forming an ionic organotin compound [ LSnPh2]+ I3− (7), which is unstable in solution and decomposes to Ph2SnI2 and 2,6-(tBuOCH2)2C6H3I (8).