C-H Bond Activation by Radical Ion Pairs Derived from R3P/Al(C6F5)3 Frustrated Lewis Pairs and N2O

Al(C6F5)(3)/R3P [R = tert-butyl (tBu), mesityl (Mes), naphthyl (Nap)] frustrated Lewis pairs react with N2O to form species, having the formula R3P(N2O)Al(C6F5)(3), which react with additional alane to generate proposed frustrated radical ion pairs formulated as [R3P.][mu.O.)(Al(C6F5)(3))(2)] that can activate C-H bonds. For R = tBu, C-H activation of a tBu group affords [tBu(2)PMe(C(CH2)Me)] [mu-OH)(Al(C6F5)(3))(2)]. In the case of R = Mes, the radical cation salt [Mes(3)P.][(mu-HO)(Al(C6F5)(3))(2)] is isolated, while for R = Nap, the activation of toluene and bromobenzene gives [(NaP)(3)PCH2Ph][(mu-OH)(Al(C6F5)(3))(2)] and [(Nap)(3)PC6H4Br][(mu-HO)(Al(C6F5)(3))(2)], respectively.