Sulphur-substituted organometallic compounds. Part IV. Reactions of p-tolylthiomethyltriphenyltin with electrophilic reagents and oxidants. Comparison of reactions of the oxygen, selenium, and germanium analogues

Abstract

Reactions of SnPh₃(CH₂ZC₆H₄Me-p)(Z = O, S, and Se) with Br₂, I₂, HgCl₂, and PhSCl generally give Sn–Ph and Sn–CH₂ bond cleavage. The following conclusions are reached: (i) all reactions of SnPh₃(CH₂OC₆H₄Me-p) lead only to Sn–Ph cleavage: (ii) no Sn–Ph bond cleavage occurs in the PhSCl reactions; (iii) the halogens give both types of cleavage on reaction with the sulphur and selenium compounds: and (iv) all reactions of HgCl₂ give only Sn–Ph bond cleavage. In contrast, the reactionsof SnPh₃(CH₂SC₆H₄Me-p) with Etl and Na[IO₄] each lead to SnPh₃(CH₂I). While attempts to prepare the tin sulphoxlde, Ph₃SnCH₂S(o)C₆H₄Me-p, have failed, the germanium analogue has been prepared using Br₂, in aqueous methanol as the oxidant. The effect on the halogen reactions of changing the aryl groups (R) in SnR₃(CH₂SR) has been briefly studied, as have reactions of GePh_3–(CH₂SC₆H₄Me-p).