Reaction of 1-alkenyl and 1-alkynyl derivatives of tin and mercury with hetero-centered radicals

Article abstract of DOI:10.1021/om00150a008

1-Alkenyl and 1-alkynyl derivatives of tin and mercury react with hetero-centered radicals such as RS^., PhSe^., PhSO₂^., or (EtO)₂P(O)^. to undergo substitution of the metal atom in a free radical chain reaction involving addition-elimination. The hetero-centered radical can be formed in a chain propagation reaction by the attack of ClHg^. or Bu₃Sn^. upon reagents such as RSSR, PhSeSO₂Ph, PhSeSePh, or PhSO₂Cl or mercurials such as Hg(SPh)₂, Hg(SePh)₂, Hg(O₂SPh)₂, or Hg[(O)P(OEt)₂]₂. In relative reactivity studies toward PhS^., vinylmercury chlorides are somewhat more reactive than the analogous tri-n-butylstannanes. Tri-n-butyl(phenylethynyl)stannane is 300 times less reactive than its β-styrenyl analogue. Toward PhS^., CH₂=CHCH₂SnBu₃ is 3 times as reactive as CH₂=CHSnBu₃ but only 1/16 as reactive as (E)-PhCH= CHSnBu₃. An explanation is advanced for the observations that PhSeSePh participates in a free radical chain substitution reaction with allylstannanes or 1-alkenylmercury chlorides but not with 1-alkenylstannanes although PhSSPh or (PhSe)₂Hg react readily with 1-alkenylmercurials or -stannanes.