Free-radical chain reactions of organic mercury and tin compounds

TL;DRAbstract

Alkylmercury halides (RHgX, R = n-butyl, n-hexyl, (DELTA)('3)-butenyl, (DELTA)('5)-hexenyl, isopropyl, cyclohexyl, cyclopentylcarbinyl and 7-norbornyl) rapidly react with PhYYPh (Y = S, Se and Te), p-MeC(,6)H(,4)SO(,2)SePh, PhSO(,2)Cl, PhSH and BrCCl(,3) under sunlamp irradiation to give RYPh, RCl, RH and RBr, respectively. The reaction is completely inhibited by di-tert-butyl nitroxide, does not occur in the dark and yields a mixture of cyclopentylcarbinyl and (DELTA)('5)-hexenyl products from the (DELTA)('5)-hexenylmercurial. The reaction is believed to proceed via a radical chain mechanism involving R(.) and Hg(III) intermediates. The alkyl radical (R(.)) undergoes S(,H)('2) or atom transfer reactions with the substrate and the resulting radical (PhY(.), PhSO(,2)(.) or (.)CCl(,3)) reacts with RHgX to form the Hg(III) intermediate which then eliminates R(.). A similar mechanism is proposed for the reaction of dialkylmercurials (R(,2)Hg, R = n-butyl, isobutyl and (DELTA)('5)-hexenyl)

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