α,ω-Bis(trichlorostannyl)alkanes: unravelling the hydrolysis pathway to organotin-oxo oligomers

New α,ω-bis(trichlorostannyl)alkanes, Cl3Sn(CH2)nSnCl3 [n = 3−5, 8], have been synthesized via tin−phenyl bond cleavage reactions on α,ω-bis(triphenylstannyl)alkanes, Ph3Sn(CH2)nSnPh3 [n = 3−5, 8], using either SnCl4 or concentrated hydrochloric acid. Some key missing links, (H2O)Cl3Sn(CH2)3SnCl3(H2O) (1a) and (H2O)2Cl3Sn(CH2)3SnCl3(H2O)2 (6), in the hydrolysis pathway of organotin trichlorides were identified. Crystal structures of the nonassociated di-tin compounds (H2O)Cl3Sn(CH2)3SnCl3(H2O) (1a) and (H2O)2Cl3Sn(CH2)3SnCl3(H2O)2 (6, isolated as the 18-crown-6 cocrystal acetonitrile solvate) as well as the polymeric hydrolysis product [H2O(OH)Cl2Sn(CH2)3SnCl2(OH)H2O·2H2O]n (7·2H2O) are reported.