REACTIVITY OF ALLYLIC AND VINYLIC SILANES, GERMANES, STANNANES AND PLUMBANES TOWARD SH2' OR SH2 SUBSTITUTION BY CARBON- OR HETEROATOM-CENTERED FREE RADICALS

Article abstract of DOI:10.1016/0022-328X(87)80119-5

Compounds of the type CH2=CHCH2MR3 and (E)-PhCH=CHMR3 (M = Si, Ge, Sn, Pb) were allowed to react with a series of heteroatom-centered radicals (PhY*, Y = S, Se, Te, derived from PhYYPh) and carbon-centered radicals ((CH3)2CH* derived from (CH3)2CHHgCl).We report that alkenylplumbanes and, under forcing conditions, alkenylgermanes undergo S_H2 or S_H2' substitution of the metal by chain mechanism analogous to those previously reported for alkenylstannanes.Alkenylsilanes are unreactive.Based solely upon product yields, the following trends were observed: The reactivity of the alkenylmetals follow the order metal = Pb > Sn > Ge (> Si).The allylmetals were more reactive then the β-metallostyrenes toward the reactants employed in this study.The chalcogen series PhYYPh exhibits the reactivity order Y = S > Se > Te.