Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions

BOUCHET, LYDIA M.; PEÑÉÑORY, ALICIA B.; PIERINI, ADRIANA B.; ARGÜELLO, JUAN E.

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Año: 2019 vol. 123 p. 5035 - 5035

1089-5639

he reactivity of sulfur and selenium centered nucleophiles towards 1-naphthyl radicals was studied in DMSO. The photostimulated reaction of sulfide anions, ?SC(NH)C6H5 (1), ?SC(NH)NH2 (2), and ?SC(NH)CH3 (3) renders, after the addition of MeI, methyl 1-naphthyl sulfide as a main product together with bis (1-naphthyl) sulfide and naphthalene under irradiation. Concordantly, the reaction of selenide anions, ?SeC(NH)C6H5 (4), ?SeC(NH)NH2 (5), ?SeCN (6), produces methyl 1-naphthyl selenide, bis (1-naphthyl) selenide and naphthalene in the presence of potassium tert-butoxide anion (entrainment conditions). Absolute rate constants for the coupling of ions 1-6 to 1-naphthyl radicals were determined; as a general trend the selenide centered nucleophiles enhance in two times the reactivity of their sulfide analogues. From the mechanistic study it is proposed that the unstable radical anion produced by the addition of the nucleophile to 1-naphthyl radical affords, after fragmentation, 1-naphthy