A study of sulphur substituted alkyltin compounds
Initially the preparation of a series of sulphidoalkyl tins Ph3Sn(C112)nSC6114-p(n-2,3 and 4) was prepared together with Ph3Sn(CI12)2C11(CI)C112SC6H4NO2-0. Their reactions with various electrophiles are detailed and compared with other functionally substituted organotins. Photolysis of the series of sulphidoalkyltins was carried out in carbon tetrachloride and volatile products identified by gc and ms-gc, while an explanation is given for the product distributions, and type. Two sulphinylalkyltins were prepared; Ph3Sn(CH2)1~S(O)Cb114Me-p (n=3 and 4), however, preparation of Ph3Sn(CH2)2S(O)C6114Me-p proved impossible. The reactions of these compounds with various electrophiles was investigated and two novel compounds isolated on reaction with mercuric chloride, namely: Ph2Sh(CII2)nS(O)C6114Me-p (n -3 and 4). The ability of these compounds to form chelated structures was also investigated and analogies drawn with other organotin chelates. A third series of compounds was prepared namely: Ph3Sn(CHL1.SO2C6114Me-p (n =2, 3 and 4). Again, the reactions of these sulphonylalkyltins with various electrophiles was studied, and the chlorodipuenyl derivatives isolated on reaction with mercuric chloride: Ph2Sn(CH2)nSO2C6H4Me-p (n =2,3 and 4). A comparison of these novel sulphido, sulphinyl, and sulphonylalkyltins is given with regard to the physical properties and the reactions displayed, while analogies are drawn with other functionally substituted organotins. Special attention is given to the elimination reaction displayed by various n-functionally substituted organotins. The relative reactivities towards iodine of Ph3Sn(C112)nS(O)m C6H4Me-p (n-2,3 and 4; m = O, I and 2) and various selenium and oxygen analogues is also detailed while an explanation is given for the varying reactivities. Reactions involving insertion into Ph - Sn bonds in various sulphur functionally substituted organotins with (COO)PdCZ2 and (Ph31')2PtC2H4 are investigated by IH NMR and 31P NMR spectroscopy, however, no solid products could be isolated. Finally the interactions of electron acceptors with sulphidoalkyltins, and various tin-sulphur bonded organotins was investigated. Stable charge transfer complexes and irreversible reactions were observed with both tetracyanoethylene and various quinones. Reaction sequences and products are also postulated.