Synthesis and structural behavior of the P-functional organotin chlorides [Ph2P(CH2)3]2SnCl2, Ph2P(CH2)3SnCl2Me, and Ph2P(CH2)nSnCl3 (n=2, 3)

The P-functional organotin dichloride [Ph2P(CH2)3]2SnCl2 (3) is synthesized by reaction of Ph2P(CH2)3MgCl with SnCl4 independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph2P(CH2)nSnCl2R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph2P(CH2)nSnCy3 (n=2, 3) with SnCl4 or MeSnCl3, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular P⋯Sn coordinations and the existence of intermolecular SnCl⋯Sn bridges. For further characterization of the title compounds, the adducts 4(Ph3PO)2 (7) and 5(Ph3PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=X⋯Sn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data.