Author:
Glover Stephen A,Novak Michael
Abstract
Properties of phenyloxenium ion 13a, phenylnitrenium ion 14a, and their 4-methyl and 4-phenyl analogues have been studied at the HF/6-31G* and pBP/DN*//HF/6-31G* levels to explain differences in their relative ease of formation and their stabilities. The phenyloxenium ions 13 are ground-state singlets but S0T1 gaps are smaller than those of the corresponding nitrenium ions. The S0 states are stabilized by donor methyl and phenyl substituents in both classes of ions, but phenyloxenium ion has much greater charge localization on the ring, primarily at the 4 position. Evidence for this difference stems from ground-state HF/6-31G*geometries, dipole moments, and vibrational frequencies. Nitrenium ions exhibit some quinoidal character, but the calculated CN bond lengths are longer than those of their 4-hydroxy-2,5-cyclohexadienone imine hydration products 17 and the symmetric C-N stretching frequencies are ca. 60100 cm1 less than those of 17. However, the CO bond lengths and stretching frequencies of the phenyloxenium ions are slightly shorter and greater, respectively, than those of their 4-hydroxy-2,5-cyclohexadienone hydration products (16). The oxenium ions are best described by their 4-oxo-2,5-cyclohexadienyl carbenium resonance structures. Accordingly, a 4-phenyl group stabilizes the phenyloxenium ion more than the phenylnitrenium ion leading to a planar geometry and considerably more charge in the distal ring, thus accounting for regioselectivities of azide reactions. Isodesmic comparisons of the energy difference between phenyloxenium and phenylnitrenium ions and their neutral hydration products explains their relative stabilities under aqueous conditions; whereas 4-biphenylyloxenium ion 13c has a lifetime in water of 12 ns as opposed to the corresponding nitrenium ion 14c (300 ns), the 4-methylphenyloxenium ion 13b is less stable to hydration by 18.7 kcal mol1 (1 cal = 4.184 J) and cannot be observed under the conditions used to generate 13c.Key words: oxenium ions, nitrenium ions, computational chemistry, nucleophilic addition, singlet state properties.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
20 articles.
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