Reactivity of the Perhaloalkanes CF2X2 (X = Cl, Br) with Nucleophiles. 6. Coexistence of Carbene and Radical Processes Initiated by Single-Electron Transfer

Article abstract of DOI:10.1021/jo00160a007

In the condensation of sodium thiophenoxide with CF2BrCl in DMF at -40 deg C, two mechanisms are involved simultaneously.A carbene chain process is postulated for the formation of C6H5SCF2Br and C6H5SCF2H.A radical chain process is implicated for the formation of C6H5SCF2Cl and C6H5SCF2SC6H5.These competitive chain processes could occur after an initial one-electron transfer from the thiophenoxide to CF2BrCl, giving a caged intimate radical/anion radical pair (RARP).