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ABSTRACT: The aniline molecule is nonplanar, with its NH2 group lying at an angle
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 Einv , and the pKa 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 CN bond length R(CN), , Einv , and the pKa , whereas
electron-withdrawing substituents have the opposite effect. Among the molecular
parameters that might serve as regression indicators for these changes, Hammett
constants, which traditionally have been used to represent substituent electronic effects,
yield fair to good correlations for R(CN) (r2 = 0.797), (r2 = 0.804), Einv (r2 = 0.829),
and the amino group pKa (r2 = 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
Qn on the amino nitrogen is well correlated with the bond length R(CN) (r2 = 0.889),
(r2 = 0.932), Einv (r2 = 0.839), and the amino group pKa (r2 = 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 Einv with both (r2 = 0.951) and
c 2000 John Wiley & Sons, Inc. Int J Quantum Chem 80: 11071115, 2000
Qn (r2 = 0.892).
Introduction
Substituents can be expected to alter the outof-plane (OOP) angle in a characteristic manner
depending on their electron-donating and -withdrawing influences. On the basis of resonance theory, electron-withdrawing substituents, especially
at the para position, should favor quinoid resonance
structures, which are more planar than aniline itself,
decreasing both and the CN bond length [7].
Methods
Conversely,
electron-donating
substituents
should favor Kekul-type structures with more
nearly tetrahedral conformations at the nitrogen atom, and hence engender greater and
R(CN) values. This same reasoning suggests that
electron-withdrawing substituents should decrease
the energetic barrier to inversion at the amino
group, Einv , and the acid dissociation pKa , whereas
1108
Results
To simplify the analysis of substituent effects, we
restricted attention to four representative properties: two structural features, the CN bond length
at the second-order MllerPlesset (MP2) level using the optimized HF 6-311G geometry. In agreement with earlier observations [28, 29] the MP2
calculation increased the barrier height by about
0.8 kcal/mol and led to a value (2.29 kcal/mol)
somewhat higher than the experimental value.
Also listed in Table I are the Mulliken, electrostatic, and natural charges on the nitrogen atom as
calculated at the various levels of theory. The variations of these charges calculated by the different
methods are illustrated in Figure 1. Here the semiempirical methods give quite small values for both
the Mulliken and natural charges on the nitrogen
atom, whereas the ab initio techniques give consistently larger values. (Note that the Mulliken and
natural charges are identical at the semiempirical
level.) The electrostatic charge is more consistent
over the different methods. Considering just the ab
initio values, the Mulliken charges still show considerable dependence on the basis set employed,
whereas the electrostatic and natural charges are relatively insensitive to changes in the basis set.
SUBSTITUENT EFFECTS
For this analysis all determinations were carried
out at the HartreeFock 6-311G level, with the
exception of the inversion barrier, which was determined at both the HF 6-311 and MP2 levels.
Calculated results for R(CN) and for aniline
and 18 of its meta- and para-substituted derivatives are shown in Table II. The variations observed
for the bond length R(CN) upon substitution are
seen to be relatively small. Electron-donating substituents tend to slightly increase R(CN), whereas
electron-withdrawing substituents slightly decrease
TABLE I
Properties and charge indices for aniline calculated at different levels of theory.
AM1
MNDO/d
PM3
B3LYP 6-31G
B3LYP 6-31G
B3LYP 6-311G
HF 3-21G
HF 6-31G
HF 6-31G
HF 6-311G
Exptl
R(CN) ()
(deg)
Einv (kcal/mol)
QM
Qe
Qn
1.400
1.423
1.430
1.400
1.398
1.396
1.376
1.397
1.394
1.396
1.402
39.19
48.35
46.40
41.35
40.36
39.36
0.11
42.72
40.94
41.73
37 46
1.00
4.22
4.47
1.21
1.01
0.92
0.00
1.63
1.29
1.45
1.50
0.327
0.228
0.071
0.786
0.656
0.468
0.984
0.889
0.740
0.527
n/a
0.956
0.857
0.746
0.822
0.797
0.763
1.094
0.944
0.922
0.851
n/a
0.327
0.228
0.071
0.836
0.848
0.782
0.885
0.879
0.894
0.814
n/a
1109
FIGURE 1. Variations in the Mulliken charge QM , the electrostatic charge Qe , and the natural charge Qn values when
calculated at different levels of theory.
this bond length. As expected, meta substituents exert a smaller influence than do para substituents, although, with the exception of the p-amino, p-cyano,
and p-nitro groups, even the para substituents have
generally little effect on the CN bond length.
A fair correlation between R(CN) and the Ham-
TABLE II
Calculated property and charge values for aniline derivatives, with experimental pKa s.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
1110
H
m-amino
m-bromo
m-chloro
m-cyano
m-fluoro
m-hydroxy
m-methoxy
m-methyl
m-nitro
p-amino
p-bromo
p-chloro
p-cyano
p-fluoro
p-hydroxy
p-methoxy
p-methyl
p-nitro
R(CN) ()
(deg)
Einv (HF)
(kcal/mol)
Einv (MP2)
(kcal/mol)
pKa
QM
Qe
Qn
1.3961
1.3929
1.3913
1.3906
1.3906
1.3890
1.3914
1.3936
1.3952
1.3902
1.4073
1.3923
1.3933
1.3810
1.3995
1.4055
1.4048
1.3991
1.3762
41.73
41.34
40.33
40.20
39.91
39.65
40.66
41.27
41.77
39.64
45.32
40.70
41.00
36.32
42.88
44.70
44.77
43.13
34.22
1.454
1.364
1.210
1.188
1.163
1.112
1.239
1.326
1.424
1.159
2.247
1.260
1.316
0.723
1.703
2.067
2.044
1.651
0.537
2.285
2.458
1.990
1.977
1.823
2.030
2.288
2.374
2.332
1.731
2.925
2.130
2.164
1.589
2.461
2.772
2.762
2.413
1.488
4.58
4.88
3.51
3.34
2.76
3.59
4.17
4.20
4.69
2.50
6.08
3.91
3.98
1.74
4.65
5.50
5.29
5.12
1.02
0.00
0.16
0.39
0.37
0.56
0.34
0.12
0.12
0.07
0.71
0.66
0.23
0.23
0.66
0.06
0.37
0.27
0.17
0.78
0.5264
0.5276
0.5249
0.5249
0.5319
0.5247
0.5260
0.5257
0.5299
0.5257
0.5297
0.5267
0.5266
0.5292
0.5259
0.5261
0.5281
0.5297
0.5258
0.8499
0.8209
0.8431
0.8302
0.8438
0.8523
0.8548
0.8416
0.8605
0.8442
0.8965
0.8491
0.8388
0.8414
0.8357
0.8028
0.8370
0.8438
0.8475
0.8143
0.8136
0.8114
0.8113
0.8109
0.8118
0.8128
0.8135
0.8144
0.8109
0.8157
0.8121
0.8124
0.8085
0.8141
0.8151
0.8152
0.8147
0.8067
FIGURE 2. Correlations of the properties examined with the Hammett constants of the substituents: (a) The amino
group CN bond distance vs. , (b) the out-of-plane angle vs. , (c) the inversion barriers E(HF)inv and E(MP2)inv
vs. , and (d) the amino group pKa vs. .
F = the F statistic for the regression.) This is illustrated in Figure 2.
The para substituents show a much better correlation with R(CN) (r2 = 0.941) than do the meta
substituents (r2 = 0.554). Unfortunately, very little
reliable gas-phase experimental data is available for
the geometries of substituted anilines [30], and Xray structures are unreliable for the present purpose
because of the influence of crystal packing forces.
As shown in Table II, substituents have a greater
effect on the OOP angle than on the CN
bond length. Although meta substitution has little
influence on , para substitution causes a significant change, with electron-donating substituents
increasing and electron-withdrawing substituents
decreasing this angle. This variation is exemplified
by the correlation of our calculated values for with
the Hammett constants of the substituents:
= 6.25(0.75) + 42.0(0.3)
n = 19,
r2 = 0.804,
s = 1.18,
F = 70.
1111
r2 = 0.931,
s = 0.34,
F = 231.
FIGURE 3. Correlations of the properties examined with the amino nitrogen atom natural charge Qn : (a) The amino
group CN bond distance vs. Qn , (b) the out-of-plane angle vs. Qn , (c) the inversion barriers E(HP)inv and E(MP2)inv
vs. Qn , and (d) the amino group pKa vs. Qn .
1112
R(CN)
Einv (HF)
Einv (MP2)
pKa
QM
Qe
Qn
R(CN)
Einv (HF)
Einv (MP2)
pKa
QM
Qe
Qn
1
0.993
0.992
0.935
0.934
0.893
0.198
0.041
0.943
0.993
1
0.975
0.941
0.956
0.897
0.186
0.027
0.966
0.992
0.975
1
0.944
0.922
0.910
0.212
0.065
0.916
0.935
0.941
0.944
1
0.974
0.975
0.146
0.050
0.944
0.934
0.956
0.922
0.974
1
0.965
0.160
0.071
0.980
0.893
0.897
0.910
0.975
0.965
1
0.242
0.126
0.918
0.198
0.186
0.212
0.146
0.160
0.242
1
0.301
0.182
0.041
0.027
0.065
0.050
0.071
0.126
0.301
1
0.059
0.943
0.966
0.916
0.944
0.980
0.918
0.182
0.059
1
r2 = 0.960,
s = 0.26,
F = 404.
Discussion
It is apparent from the information in Table III that the variations caused by substitution in
the four properties examined are closely tied together. As one would anticipate from general prin-
1113
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