Generation and Trapping of the 4-Biphenylyloxenium Ion by Water and Azide:  Comparisons with the 4-Biphenylylnitrenium Ion

Generation of the 4-biphenylyloxenium ion, 1a, from hydrolysis of 4-acetoxy-4-phenyl-2,5-cyclohexadienone, 2a, is demonstrated by common ion rate depression and azide trapping. The ion is less selective with a shorter lifetime (12 ns at 30 °C) in aqueous solution than the corresponding nitrenium ion, 6a (ca 0.3 μs at 30 °C). Its lifetime is considerably longer than those of structurally related carbenium ions. Unlike 6a, 1a reacts with N3 -, in part, at the distal ring to generate 4‘-azido-4-hydroxybiphenyl, 5. These results are rationalized by calculations at the HF/6-31G* and pBP/DN*//HF/6-31G* levels that show that 1a is planar but is less stable than 6a relative to their hydration products by ca. 12 kcal/mol. The p-tolyloxenium ion, 1b, has not been unequivocally demonstrated to be formed in H2O, but kinetic data show that it must be at least 104-fold less stable than 1a relative to their respective 4-acetoxy derivatives. It is also calculated to be ca. 19 kcal/mol less stable than the corresponding nitrenium ion, 6b, relative to their hydration products.