G2(MP2,SVP) STUDY OF THE RELATIONSHIP BETWEEN THE BENZYL AND TROPYL RADICALS, AND THEIR CATION ANALOGS

The calculated heat of formation and ionization energy of the benzyl r adical at the G2(MP2,SVP) level differ from recent experimental estima tes by just 1 kJ mol(-1). The ionization energy of the tropyl radical calculated at this level differs from experiment by 5 kJ mol(-1). The heat of formation of tropyl, 281 +/- 8 kJ mol(-1), is significantly hi gher than experimental estimates, suggesting the need for experimental re-evaluation. The lowest energy path for rearrangement of the benzyl cation to tropylium proceeds through a single intermediate minimum, t he 1-cycloheptatrienyl cation, and requires 272 kJ mol(-1). (C) 1997 P ublished by Elsevier Science B.V.