Substituent effects on the physical properties and pKa of aniline

✍ Scribed by Kevin C. Gross; Paul G. Seybold

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 199 KB
• Volume: 80
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/1097-461x(2000)80:4/5<1107::aid-qua60>3.0.co;2-t

✦ Synopsis

The aniline molecule is nonplanar, with its NH 2 group lying at an angle θ of approximately 42 • to the plane of the benzene ring. Substituents on the phenyl ring alter this out-of-plane angle as well as other molecular properties such as the ring bond lengths and angles, the barrier to inversion E inv , and the pK a of the amino group. Ab initio 6-311G * * quantum chemical calculations have been employed to examine these substituent influences and the extent to which they are interrelated. Electron-donating substituents increase the C-N bond length R(C-N), θ, E inv , and the pK a , whereas electron-withdrawing substituents have the opposite effect. Among the molecular parameters that might serve as regression indicators for these changes, Hammett σ constants, which traditionally have been used to represent substituent electronic effects, yield fair to good correlations for R(C-N) (r 2 = 0.797), θ (r 2 = 0.804), E inv (r 2 = 0.829), and the amino group pK a (r 2 = 0.931) for aniline and 18 substituted anilines. Of several measures of atomic charge, the Mulliken and electrostatic charges on the amino nitrogen atom show essentially no correlation with these properties. In contrast, the natural charge Q n on the amino nitrogen is well correlated with the bond length R(C-N) (r 2 = 0.889), θ (r 2 = 0.932), E inv (r 2 = 0.839), and the amino group pK a (r 2 = 0.960). This latter result suggests that the natural charge, rather than either the Mulliken or electrostatic charges, may be the preferred charge descriptor for correlation purposes. Inclusion of electron correlation at the MP2 level increases the correlations of E inv with both σ (r 2 = 0.951) and Q n (r 2 = 0.892).