title: Mechanism of S(H)2 reactions of disulfides: frontside vs backside, stepwise vs concerted.
abstract: Density functional theory calculations indicate that the S(H)2 reactions of disulfides with alkyl or aryl radicals take place via concerted backside displacement. The activation energies for reactions of Me* with RSSR (R = Me, Et, (i)Pr, (t)Bu) increase with the size of R, since larger R groups prevent the formation of an ideal geometry for SOMO-LUMO overlap. Frontside transition states can also be located, but these lie at least 11 kcal mol(-1) above the corresponding backside transition states.
authors: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
authors: Elizabeth H
authors: EH
authors: Krenske
authors: William A
authors: WA
authors: Pryor
authors: K N
authors: KN
authors: Houk
mesh_terms: D003198:Computer Simulation; D004220:Disulfides / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D008956:Models, Chemical
chemical_list: D004220:Disulfides; D005609:Free Radicals