Ja 021307 W
Ja 021307 W
Ja 021307 W
Abstract: The mechanism of electrophilic aromatic nitration was revisited. Based on the available
experimental data and new high-level quantum chemical calculations, a modification of the previous reaction
mechanism is proposed involving three separate intermediates on the potential energy diagram of the
reaction. The first, originally considered an unoriented -complex or electron donor acceptor complex (EDA),
involves high electrostatic and charge-transfer interactions between the nitronium ion and the -aromatics.
It explains the observed low substrate selectivity in nitration with nitronium salts while maintaining high
positional selectivity, as well as observed oxygen transfer reactions in the gas phase. The subsequent
second intermediate originally considered an oriented -complex is now best represented by an intimate
radical cation-molecule pair, C6H6+/NO2, that is, a SET complex, indicative of single-electron transfer
from the aromatic -system to NO2+. Subsequently, it collapses to afford the final -complex intermediate,
that is, an arenium ion. The proposed three discrete intermediates in electrophilic aromatic nitration unify
previous mechanistic proposals and also contribute to a better understanding of this fundamentally important
reaction. The previously obtained ICR data of oxygen transfer from NO2+ to the aromatic ring are also
accommodated by the proposed mechanism. The most stable intermediate of this reaction on its potential
energy surface is a complex between phenol and NO+. The phenolNO+ complex decomposes affording
C6H6O+/PhOH+ and NO, in agreement with the ICR results.
Introduction
(1) (a) Considered as Electrophilic Aromatic Substitution, Part 67. For part
66, see: Salzbrunn, D.; Simon, J.; Prakash, G. K. S.; Petasis, N. A.; Olah,
G. A. Synlett 2000, 10, 1485. (b) Taylor, R. Electrophilic Aromatic
Substitution; John Wiley & Sons: Chichester, U.K., 1990.
(2) (a) Olah, G. A.; Malhotra, R.; Narang, S. C. Nitration Methods and
Mechanisms; VCH: New York, 1989. (b) Cardoso, S. P.; Carneiro, J. W.
M. Qum. NoVa 2001, 24, 381-389.
(3) Ingold, C. K. Structure and Mechanism in Organic Chemistry; Cornell
University Press: New York, 1969.
(4) (a) March, J. AdVanced Organic Chemistry; John Wiley & Sons: New
York, 1985. (b) Lowry, T. H.; Richardson, K. S. Mechanism and Theory
in Organic Chemistry; Harper and Row: New York, 1987.
(5) Aschi, M.; Attina`, M.; Cacace, F.; Ricci, A. J. Am. Chem. Soc. 1994, 116,
9535.
(6) Peluso, A.; Del Re, G. J. Phys. Chem. 1996, 100, 5303.
(7) Lund, T.; Eberson, L. J. Chem. Soc., Perkin Trans. 2 1997, 1435.
(8) Ingold, C. K.; Hughes, E. D. J. Chem. Soc. 1950, 2400.
4836
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Scheme 3 . Single-Electron-Transfer Mechanism for Electrophilic
Aromatic
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Esteves et al.
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Figure 1. Geometries for NO2+/benzene complexes 1-7 obtained with energy minimization procedures at the B3LYP/6-31++G** level.
tion for the new species. In the second case, the bonds involved
in the reaction change concomitantly with the electron transferred from one reactant to the other. At some point, the singleelectron transfer and the two-electron (polar) mechanism merge,
since they represent the two extremes of a possible continuum.
To investigate in more detail the still challenging problem
of the mechanism of electrophilic nitration of aromatics, we
carried out detailed quantum chemical calculations of the
reaction of NO2+ with selected aromatics. For comparison,
similar calculations were also performed with representative
olefins.
H (298 )
(kcal/mol)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
17.71
22.71a
14.30
0.73
9.68a
7.50
1.12
0.00
5.77a
1.56
8.63
6.55
5.51
-5.96
-7.67
11.97
16.45
14.58
5.22
30.36
-47.02
11.18
species
H (298 )
(kcal/mol)
23
24
25
26
27
28
29
30
31
32
33
34
35
36
34
NO2+ + C6H6
NO2 + C6H6+
NO + C6H6O+
C6H6NO2 + H+
PhOH + NO+
PhOH+ + NO
-4.38
-5.72
-3.93
-24.71
-32.81
10.82
5.84
5.94
17.22
22.81
12.49
14.20
20.15
7.74
8.26
33.54
11.70
35.76
159.41
4.27
-29.74
B3LYP/6-311++G**//MP2(full)/6-31++G**.
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Esteves et al.
Figure 2. Geometries for products 8-13 of NO2+/benzene obtained with energy minimization procedures at the B3LYP/6-31++G** level.
Figure 3. Geometries for products 14-20 of NO2+/benzene obtained with energy minimization procedures at the B3LYP/6-31++G** level.
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Figure 4. Geometries for products 21-25 of NO2+/benzene obtained with energy minimization procedures at the B3LYP/6-31++G** level.
Figure 5. Geometries for products 26-30 of NO2+/benzene obtained with energy minimization procedures at the B3LYP/6-31++G** level.
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Esteves et al.
Figure 6. Geometries for the transition states 31-37 connecting the several intermediates, calculated at B3LYP/6-31++G** level.
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Figure 7. Pictorial representation of the potential energy surface of benzene with NO2+.
Table 2. Atomic Charges (ChelpG) and Morokuma Decomposition
Analysis Interaction of Benzene with the Nitronium Ion Interaction
for the Complexes 3 and 4
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Figure 8. Frontier molecular orbital analysis and its relation with single-electron-transfer nitration.
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NO2 f NO2+ + e
NO f NO+ + e
benzene f C6H6+ + e
nitrobenzene f C6H5NO2+ + e
1,2-dinitrobenzene f C6H4N2O4+ + e
1,3-dinitrobenzene f C6H4N2O4+ + e
1,4-dinitrobenzene fC6H4N2O4+ + e
fluorbenzene f C6H5F+ + e
chlorobenzene f C6H5Cl+ + e
bromobenzene f C6H5Br+ + e
iodobenzene f C6H5I+ + e
C6H5CN f C6H5CN+ + e
C6H5CF3 f C6H5CF3+ + e
o-C6H4F2 f o-C6H4F2+ + e
m-C6H4F2 f m-C6H4F2+ + e
p-C6H4F2 f p-C6H4F2+ + e
o-C6H4Cl2 f o-C6H4Cl2+ + e
m-C6H4Cl2 f m-C6H4Cl2+ + e
p-C6H4Cl2 f p-C6H4Cl2+ + e
PhOH f PhOH+ + e
PhOMe f PhOMe+ + e
toluene f C7H8+ + e
mesitylene f C9H12+ + e
PhNH2 f PhNH2+ + e
naphthalene f C10H8+ + e
CH4 f CH4+ + e
C2H6 f C2H6+ + e
C3H8 f C3H8+ + e
i-C4H10 f i-C4H10+ + e
a
ionization energya
(IE) (eV)
9.586 ( 0.002
9.2642 ( 0.00002
9.24378 ( 0.00007
9.94 ( 0.08
10.71
10.4
10.3 ( 0.1
10.50 ( 0.02
10.63 ( 0.10
10.65
9.20 ( 0.01
9.07 ( 0.02
9.00 ( 0.03
8.72 ( 0.04
9.73 ( 0.01
9.685 ( 0.005
9.29 ( 0.01
9.33 ( 0.02
9.1589 ( 0.0005
9.06 ( 0.02
9.10 ( 0.02
8.92 ( 0.03
8.49 ( 0.02
8.20 ( 0.05
8.828 ( 0.001
8.40 ( 0.01
7.720 ( 0.002
8.1442 ( 0.0009
8.141 ( 0.01
12.61 ( 0.01
11.52 ( 0.04
10.94 ( 0.05
10.68 ( 0.11
0.000
-0.322
-0.342
+0.354
+1.124
+0.814
+0.714
0.00
-7.42
-7.89
+8.16
+25.92
+18.77
+16.5
-0.386
-0.516
-0.586
-0.866
+0.144
+0.099
-0.296
-0.256
-0.427
-0.526
-0.486
-0.666
-1.096
-1.386
-0.758
-1.186
-1.866
-1.442
-8.90
-11.9
-13.5
-20.0
+3.32
+2.28
-6.83
-5.90
-9.85
-12.13
-11.21
-15.36
-25.27
-31.96
-17.48
-27.35
-43.03
-33.25
+3.024
+1.934
+1.354
+1.094
+69.73
+44.60
+31.22
+25.22
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Figure 10. Electrostatic complexes formed by the interaction of benzene with related electrophiles and model compound COS.
Activation of strongly deactivated aromatics such as nitrobenzene and trifluoromethylbenzene (C6H5CF3) as well as that of
alkanes via single-electron transfer to the nitronium cation is,
however, unfavorable (IE > 0). Nevertheless, halobenzenes
and dihalobenzenes are indicated to be able to undergo oxidation
by NO2+ (IE < 0) through a SET mechanism, which could
alternatively explain the observed unusual ortho/para selectivity
in their electrophilic nitrations.44 It should be pointed out that
solvent effects and interaction with the counterion can change
the ionization energies, especially for the nitronium ion; this
could result in themodynamically favorable gas-phase reactions
becoming unfeasible or vice-versa. It is therefore reasonable to
expect that these effects could change the mechanism from an
SET to a polar two-electron-transfer reaction, and their role
should not be ignored.
If the rate-determining step involves electron transfer, isotope
effects should not affect the rate (if one considers the models
of nonlocalized electrons and vertical transitions); thus, kH/kD
should be 1. Using ICR techniques for studying these reactions
in the gas phase, Olah and co-workers found no isotope effect
(i.e., kH/kD ) 1).30 This could mean that the reaction is driven
in this case by single-electron transfer. Olah and collaborators
have also shown that the nitration of benzene and its isotopomers
with NO2+BF4- salts in CH2Cl2 solution gave an inverse
secondary isotopic effect (kH/kD ) 0.86).45a-c Hence, a singleelectron-transfer mechanism cannot be the rate-determining step
in this case. It follows that the lowest energy path in the gas
phase and in solution may involve differing rate-determining
steps. Since substrate selectivity is also low in this case, the
rate-determining step is considered to be the formation of the
electrostatic donor-acceptor complex, proposed originally by
Olah2a as the unoriented -complex.
Interaction of Benzene with Other Electrophiles and
Model Compounds. To better understand the effect of electrostatic interactions, we subsequently performed DFT calculations of the interaction between benzene with other electrophiles
that configurationally resemble NO2+, namely NO+, CO2
(isoelectronic to NO2+), and acetyl and formyl cations (H3CCO+, HCO+) as well as the model molecule COS. Complexes
which were characterized as minima are shown in Figure 10.
A recent theoretical study by Heidrich45d has shown that whereas
the isopropyl cation with benzene forms a -complex as the
(44) See ref 4a, p 509-510.
(45) (a) Reference 2a, p 140. (b) Hunziker, E.; Myhre, P. C.; Penton, J. R.;
Zollinger, H. HelV. Chim. Acta 1975, 58, 230. (c) Olah, G. A. J. Tenn.
Acad. Sci. 1965, 40, 77. (d) Heidrich, D. Angew. Chem., Int. Ed. 2002, 41,
3208. (e) Solca`, N.; Dopfer, O. Angew. Chem., Int. Ed. 2002, 41, 3628.
4846 J. AM. CHEM. SOC.
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Figure 11. Structures VI, VIII, IV, I, V, XIV, and XV from ref 48.
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