Journal of Molecular Structure, 86 (1982) 301-314

THEOCHEM
Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

QUANTITATIVE FRONTIER ORBITAL THEORY

Part I. Electrophilic aromatic substitution

ROBERT J. ELLIOTT, VALERIE SACKWILD and W. GRAHAM RICHARDS

Physical Chemistry Laboratory, Oxford University, South Parks Rd., Oxford OX1 3QZ
(Gt. Britain)

(Received 18 March 1981)

ABSTRACT

An ab initio version of frontier orbital theory which employs the charges within
defined regions of space associated with particular orbitals is described. It is then applied
to nitration of a wide range of aromatic molecules.

INTRODUCTION

Rationalisation of the effects of substituents on the rates and orientations

of aromatic substitution reactions has been a problem which has persistently
intrigued organic and theoretical chemists alike. It is made difficult, as are all
considerations of chemical reactivity, by our inability to make direct obser-
vation of transition states, and hence to know their structures. The traditional
approach has been to look instead at the intermediate [l] of the reaction
(the “product” of the rate-determining stage; Hammond’s postulate tells us that
this will be more like the transition state than the reactant, due to its endo-
thermic formation). Valence bond structures are used to assess the stability
of possible intermediates and substituents are classified as activating or
deactivating, and ortho-, para- or meta-directing, on this basis.
This approach works quite well for simple molecules but cannot deal with
many more complicated cases or with substituents which resist such simple
classification. Perturbation molecular orbital theories [ 21 (which attempt to
simulate the transition state) and the concept of localisation energy [3] have
both been applied with some success, but these can only be used in conjunc-
tion with very simple and approximate calculations. The frontier orbital
theory [4], however, can be applied with molecular orbital calculations of
any complexity. This theory is based on the assumption that reaction should
occur at the position of highest density of electrons in the frontier orbitals,
which are defined according to the reaction type; for an electrophilic
reaction we take the highest occupied molecular orbital (HOMO), for a
nucleophilic reaction the lowest unoccupied molecular orbital (LUMO), and
for a radical reaction both of these. Usually only semi-empirical calculations

0166-1280/82/0000-0000/$02.75 o 1982 Elsevier Scientific Publishing Company

302

are used, but some good correlations with experimental data are nevertheless
obtained. The book by Fleming [4] deals with this subject in detail.
While the calculations used are evidently of great value, they have not
been applied to a comprehensive series of specific aromatic molecules. In the
very simplest methods (HMO), all the u electrons in the molecule are ignored.
This is obviously unsatisfactory since in reality one cannot distinguish
between u and 71 electrons. In the more sophisticated semi-empirical calcula-
tions, u electrons are included, but only by sacrificing accuracy or by using
rather daring parameterisations. Further, since the parameters employed are
often estimated from experimentally determined quantities such as ionisation
potentials, the predictive value is not so great as is often claimed. The use of
atomic orbital coefficients is also suspect; an attacking electrophile will see
the molecule as a whole, not as a collection of isolated atomic centres. The
difference in A0 coefficients between two atoms might be large but the
charge distribution in their vicinity could be such that discrimination
between the sites was not possible.
We have applied ab initio calculations (in which all integrals are calculated
explicitly using a self-consistent field procedure) to frontier orbital theory.
Precisely defined and localised orbital charge densities are obtained from the
molecular wavefunctions and correlated with reactivity in a wide range of
compounds. Since the method used is not subject to the objections cited
above, we believe the results to be of significant value in the theoretical
description of electrophilic substitution reactions.

METHODS

The calculations were performed on a CDC 7600 computer using the

Gaussian 76 program [ 51 with an STO-3G basis set [6] . Experimental geo-
metries were used when available, otherwise average bond lengths and angles
for the particular molecular environment were taken [ 71. Charge densities
for each atom in a molecule are usually assigned by the Mulliken population
analysis [8], which partitions the charge among the atoms in an essentially
arbitrary manner. We use instead the novel method of Dean and Richards [9]
and calculate the charge in a sphere of chosen radius which may be centred any-
where on or around the atoms in the molecule. The computation is simple;
the wavefunction is squared, in accordance with Born’s probabilistic inter-
pretation, and integrated over the required volume, the co-ordinate origin
being set at the centre of the sphere. (The program is to be made available
by the QCPE.) The charge obtained varies almost linearly [lo] over the
range of radii of chemical interest, so for a series of compounds any conclu-
sions will be unaffected by the exact value of radius chosen.
A thorough comparison of this method with other sources of localised
charges has been made [ll] and it has been shown to be superior in many
important respects. The division of charge is much more meaningful
physically; unlike the other methods all the charge is not assigned to the
 303

constituent atoms in the molecule. The use of off-centres (spheres which

are not centred on a particular atomic nucleus) considerably extends the
applicability of charge distributions to the study of molecular properties.
Unlike the Mulliken population analysis, the results obtained are invariant to
transformations of the basis set. A quantitative investigation of inductive effects
has already been successfully performed [lo] by the use of sphere-charges.
The molecular wavefunction is obtained in the form of a density matrix
for the molecule, whose elements are the sum over all molecular orbitals, h,
of products of the atomic orbital coefficients in the LCAO expressions
(eqn. 1). We have recently extended this so that a density matrix corresponding
to a single molecular orbital, DC’), (eqns. 2 and 3) may be obtained. A
simple modification of the program is involved which assigns occupation
numbers of zero to all orbitals other than that of interest. This allows the
calculation of sphere-charges for any orbital of interest, in addition to the
total charges. In this way a direct quantification of Fukui’s original concept
of the “highest density of electrons in the frontier orbitals” can be obtained
and ab initio frontier orbital theory may be performed. The method is
highly suited to the study of orientation effects, having the obvious advantage
that it takes into account the nodal properties of the orbital in the vicinity
of the atom in question, whereas coefficients do not.

Dij = 1 CikCjk
(1)
k
D!!‘= C.
rk
C.
Ik (2)
11

Dij = x 0;;’ (3)

k

RESULTS AND DISCUSSION

It is convenient to divide substituents into three categories; those with

heteroatoms capable of donating a pair of electrons into the ring, those which
withdraw electrons from the ring, and simple conjugated systems such as
vinyl or phenyl. We designate these as X-, Z- and C-substituents respectively.
Simple alkyl groups are included in the first category since overlap of u-bonds
with the n-system (hyperconjugation) may be regarded as analogous to the dona-
tion of lone pairs (although it is a much smaller effect).
The simplest way to proceed is to take the benzyl cation, benzyl anion
and styrene as models for Z-, X- and C-substituted benzenes respectively.
The relevant frontier orbital energies and sphere-charges for these compounds
are given in Fig. 1. The spheres are chosen to have a radius of 0.7 ,& (half the
C-C internuclear distance) and are centred on the carbon nuclei. It can be
seen that the total charges mirror the broad directive effects of the substi-
tuents; X- and C-substituents are ortho- and pare-directing, Z-substituents
are metu-directing. The HOMO charges give the same result as simple
frontier orbital theory (Fig. 1); a much better correlation is obtained for the
304

+/
hi?
TOTAL 4 7094
HOMO ~0021
NHOMO 0 2371

TOTAL 4 6853
/HOMO
0 2332
WHOM0 0 0069
cb
/ --HOMO
TOTIL 4.0572
0 0606
““On0 o-1341
f@
DI
TOTAL3.8315
* “HOMO 0 1813
WHOHO 0 0109

TOTAL4
w
/
6661
&L 4-7221
“OH0 0 2196
nHOn0 0 ,241 TOTAL
4
/
0632
m:ALco3l7
non0 0 0041
“HO”0 0 0479
HOMO 0 0020 HOHO 0 0496
NHO”0 0 2603 NHOMO 0 3304

I Benzyl cation II Benzyl anion III Styrene

HOMO energy (ax.) -0.4831 + 0.1420 -0.2468

NHOMO energy (a.u.) -0.5145 -0.0597 -0.2792
Hiickel coefficients 1-o 0 -0.334
o-o.5 -0.378 -0.308
m-o.5 0 0.130
P-0 0.378 0.394
0 0.394
P 0.595

Fig. 1. Models for substituted benzenes.

benzyl anion and styrene but a poorer one for the benzyl cation. This problem
is usually surmounted, in simple theory, by supposing that the next-highest
molecular orbital (NHOMO) is too low-lying to be ignored. It is included by
defining a frontier electron population [ 121, F, given by

CZHOMO+ &rOMO e-oL

F=2 (4)
1 _ e-DL

where the c’s are the orbital coefficients, L is the energy separation of the
HOMO and NHOMO in units of the Hiickel resonance integral, and D is a
parameterised constant, which is usually given the value 3.
The HOMO and NHOMO may be represented schematically as in Fig. 2,
where the size of the spheres is meant to correlate roughly with the magni-
tude of the orbital coefficients or sphere charges. In benzene these two
orbit& are degenerate, so we add together the corresponding charges to
give an equal value for each carbon atom. The presence of the substituent
perturbs the system and therefore the degeneracy is removed [ 131. The
energy of (i) will not be much affected since the charge at the position
of substitution is small (in benzene itself this is a node). However (ii) will be
stabilised by an acceptor substituent and destabilised by a donor substituent.
Hence the HOMO of a Z-substituted benzene is (i), and we find high charges
at the ortho and meta positions. Mixing in some of the NHOMO will tend to
increase the meta charge at the expense of the ortho, due to the greater
effect of the substituent at the ortho position. Similary a C- or X-substituted
benzene has (ii) as its HOMO; inclusion of the NHOMO will tend to increase
the ortho and meta charges at the expense of the paru; this is most marked at
the ortho position where the substituent effect is greater.
 305

Fig. 2. HOMO and NHOMO of a substituted benzene.

We have employed a semi-empirical approach in which a maximum

separation for NHOMO inclusion is chosen to produce the best correlations.
By investigation of a wide variety of compounds a value of 0.036 a.u. was
obtained, and we now define a frontier charge density, Fq, by
0.036 -D
FP = ~HOMO + qNHOM0 (5)
0.036
where q is the appropriate sphere charge and D is the HOMO-NHOMO
separation in atomic units. In systems where the separation is greater than
0.036 a.u. the frontier charge density is defined as the HOMO sphere charge
alone. The results for the benzyl cation and styrene are given in Fig. 3; the
agreement with experiment is good.
These ideas have been extended to a wide range of specific substituted
benzenes; a summary of our results is given in Table 1, together with a com-
parison with experiment [ 14,151. In cases where the symmetry of the mol-
ecule is affected by the conformation of the substituent the mean of the
calculated ortho and metu charges is taken.
The following points should be noted.
(1) For the simpler compounds (i.e. monosubstituted benzenes), reason-
ably good correlations with experiment are obtained for both the total and
the frontier sphere charges. However, for more complicated molecules,
correlation with the total charges is either poor or non-existent, while with
the frontier charges it is very good.
(2) The frontier charges tend to give a much better indication of the
relative proportions of o- and p-products than the total charges, and often
correctly indicate the formation of substantial amounts of products not pre-
dicted by the assumed directive effects (e.g. V, XIII, XVI).
(3) Frontier charges give good correlations in those cases where a substi-
tuent cannot be classified as either o-, p- or m-directing (e.g. in XII, substantial
substitution at all three positions is correctly predicted).

Fig. 3. Frontier charge densities for styrene and benzyl cation.

306

TABLE 1

Total and frontier sphere charges for aromatic molecules

Compound HOMOenergy NHOMOenergy Total Frontier % Nitration

(au.) (&IL) spherecharge chargedensity
(electrons) (electrons)

Iv +I.2783 -0.2783 4.0206 0.3033

V W
o-4.0284 0.2507 58.8
AI.2658 4.2762 m-4.0195 0.2289 4.4
p-4.0236 0.2918 36.8

VI 0CH3
o-4.0328 0.1102 20.0
-0.2429 a.2813 m-4.0174 0.0440
p-4.0240 0.2480 80.0

VII
o-4.0350 0.1757 12.4
a.2652 -0.2894 m-4.0143 0.1281
p-4.0256 0.2752 87.6

VIII CF3
o-4.0191 0.2928
-0.2928 -0.2948 m-4.0192 0.3003
p-4.0170 0.2812

IX NO2
o-4.0120 0.0061 6.4
a.2766 4.3117 m-4.0172 0.0062 93.2
p-4.0116 0.0001 0.25

X
o-4.0191 0.2066 30.1
-0.2837 -0.2996 m-4.0162 0.1797
p-4.0184 0.2520 69.9

XI CHzCl
o-4.0189 0.2701 40.9
4.2829 -0.2885 m-4.0152 0.2591 4.2
p-4.0154 0.2860 54.9

XII CHCI,
o-4.0185 0.2951 23.3
4.2942 -0.2947 m-4.0151 0.2970 33.8
p-4.0134 0.2903 42.9

XIII
O-4.0145 0.2889 6.8
-XI.3036 4.3052 m-4.0143 0.2983 64.5
p-4.0102 0.2721 28.7
 307

TABLE 1 (continued)

Compound HOMOenerw NHOMOenergy Total Frontier % Nitration

(a.u.) (al.) spherecharge chargedensity
(electrons) (electrons)

XIV NHCOCHJ
I o-4.0603 0.0936 40.1
-0.2294 4.2792 m-4.0148 0.0282
u-4.0245 0.1821 59.3

xv COzH
O-4.0103 0.2106 18.5
-a2799 4.2876 m-4.0151 0.2587 80.2
p-4.0120 0.2215 1.3

XVI
o-4.0128 0.2518 28.3
-0.2856 a.2996 m-4.0177 0.2588 68.4
p-4.0122 0.2490 3.3

XVII OH
o-4.0369 0.1130 t
-0.2442 -0.2839 m-4.0095 0.0437
p-4.0264 0.2552 +

o-4.0127 0.0716 53.0

4.2327 -0.2775 m-4.0239 0.0235
p-4.0162 0.1468 47.0

XIX C2H5
o-4.0090 0.2251 +
-0.2599 -0.2749 m-4.0295 0.1918
p-4.0155 0.2801 c

xx
o-4.0368 0.1190 e
-0.2196 -0.2749 m-4.0098 0.0305
p-4.0299 0.2247

XXI CN
o-3.9916 0.2401 17.1
-0.2946 -0.3039 m-4.0149 0.2307 80.7
p-4.0100 0.2518 2.2

XXII SOJH
o-4.0078 0.2260
-0.2581 -0.2773 m-4.0154 0.2245 +
p-4.0086 0.0207

2mII CiCH
o-4.1845 0.1358 +
-0.2599 4.2868 m-4.0199 0.0983
p-4.0187 0.2054 +
308

TABLE 1 (continued)

Compound HOMOener~?y NH0M0ene1~y Total Frontier % Nitration

(au.) (a.u.) spherecharge chargedensity
(electrons) (electrons)

XXIV W
2-4.0365 0.2430 c
-0.2594 4.2689 4-4.0316 0.2865 +
54.0187 0.2031
3

xxv
2-4.0303 0.1059 e
-0.2537 -0.2869 3-4.0185 0.0842

FsC 2-4.0229 0.2546 +

4.2790 -0.2911 4-4.0209 0.0970
54.0146 0.2302
6-4.0181 0.5007 +
Q
' = CH
3
F 2-4.0326 0.1822 +
-0.2601 4.2795 4-4.0277 0.2841 +
5-4.0150 0.1316
6-4.0277 0.2336 +
Q’ = CH3
Cl 3-4.0080 0.0157
-0.2810 -0.3105 44.0159 0.0383 t
5-4.0081 0.0038
6-4.0173 0.0193
No2

2-4.0079 0.0115 c
-0.2862 -0.3168 3-4.0164 0.0065

xxx Cl 2-4.0418 0.0870 2

4-4.0284 0.1772 59

Q' = NH 2 -0'2355
-0.2829 5-4.0052
6-4.0250
0.0348
0.2541 39

2-4.0216 0.1432 c
-0.2555 4.2814 3-4.0279 0.1342

CH3
Cl 2-4.0163 0.1937
44.0123 0.2437 100

Q
’= CHO -0’2872
+I.3014 5-4.0125
6-4.0119
0.1588
0.2225
 309

TABLE 1 (continued)

Compound HOMOenergy NHOMOenergy Total Frontier % Nitration

(a.u.) (a.u.) spherecharge chargedensity
(electrons) (electrons)

XXXIII Cl 2-4.0418 0.0870

4.2606 -~a.2931 4-4.0284 0.1772 32

Q’ = OH
5-4.0052
6-4.0250

2-4.0652
0.0348
0.2541

0.0123
68

5
4-4.0383 0.2250 20

xxxv
Q
’=
Cl
OCH 3 4’2531
4.2829 5-4.0092
6-4.0863

2-4.0104
0.0040
0.1960

0.2288
25

8.7
44.0207 0.2390 91.3

Q
’=
OH
CO
2H 4’2g85
-0.3074 5-4.0104
6-4.0115

2-4.0432
0.1732
0.2237

0.0797
a.2515 4.2868 4-4.0231 0.2516 c

Q
’ = CHO

HJc\N/cH3--. 2146
5-4.0094
6-4.0268

2-4.0652
0.0028
0.1448

0.0123
-0.2765 4-4.0383 0.2250 t
I
5-4.0092 0.0040
6-8.0863 0.1966

CO
2CH 3
NHCOCHJ 2-4.0235 0.1118
-0.2213 -0.2613 4-4.0186 0.1721 t
5-4.0123 0.0209
6-4.0692 0.0992
Q’ = NO 2
2-4.0193 0.1000
;CHz 4-4.0142 0.1739
XH -0.2730 -0.2767 5-4.0165 0.0359
6-4.0176 0.0704
7-4.3511 0.1448
g-3.8330 0.2008 t
NO2
XL 2-4.0181 0.0576
4.2288 -0.2914 3-4.0409 0.0720
7-4.3501 0.0652
8-3.8385 0.1303

XL1
3-4.0180 0.0765
NO2 5-4.0167 0.0382
-0.2767 -0.2869
6-4.0232 0.0640
310

TABLE 1 (continued)

Compound HOMO energy NHOMO energy Total Frontier % Nitration

(au.) (&IL) sphere charge charge density
(electrons) (electrons)

XLII Ok!
-0.2492 -0.2987 2-4.0169 0.05532 t
54.0723 0.09180
6-4.0186 0.01159
NO 2
NHCOCH~

XL111 NHCOCH3
cl 4.2988 -0.3078 4-4.0070 0.0309
5-4.0095 0.0539 +

Cl

(4) The frontier charges predict the formation of substantial proportions

of side-chain substitution in C-substituted benzenes, as observed (e.g. the p-
position in styrene).
The empirical rules which organic chemists apply to predict the orientation
in disubstituted cases may be readily derived from the results, i.e.:
(1) There is no problem when the substituent effects reinforce each other.
(2) When an activating and deactivating substituent are in competition
the activator normally dominates, the distribution being perturbed by the
presence of the deactivator. The slightly anomalous cases of 100% par-u sub-
stitution (e.g. XXXII) are probably due to interaction of the electrophile
with the lone pairs on the meta substituent; attack nevertheless coincides
with the highest frontier charge density.
(3) If two activating or deactivating substituents are in competition,
that with the stronger effect wins (e.g. F over CH,, XXV). An X-substituent
will usually win over a C-substituent (e.g. XL).
(4) Cases XL1 and XLIII, previously explained away as special effects
[14], are accounted for naturally by this theory.
The experimental data in Table 1 refer exclusively to nitration; for some
other electrophiles (those which are very hard) we might find better correla-
tions with total charges than with frontier charge density. For example,
toluene gives more ortho product when the attacking electrophile is Cl’. In
Table 2 we list observed ortho/2X para ratios [16], in toluene, and LUMO
energies which we have calculated for several different electrophiles. Of
these NO,’ has a LUMO which is closest in energy to the HOMO of toluene;
species higher in the list are less susceptible to orbital control and the electro-
static effect becomes dominant so that more ortho product is produced (the
total charge is greater at the ortho than at the para position). For those
electrophiles below NO,’ in the list there is no trend in LUMO energy, but
they are all relatively large and steric effects are probably responsible for the
 311

TABLE 2

o-/2p- Ratios in toluene as a function of electrophile LUMO energy

Electrophile o-/2p- LUMO energy (ax.)

OH+ 2.00 -0.4245

Cl’ 1.63 -0.5137
Br’ 1.29
H’ 1.06-0.3 +0.3080
NO; 0.72 -0.2419
Cl, 0.97-0.25 0.1245
Et+ 0.47 4.7008
so, 0.25 0.1488
HgOAc’ 0.25
Br, 0.25-0.11
CH,CO+ 0.0006 4.8234

high proportions of par-u products produced. In the majority of cases, and in

all the disubstituted cases which we have investigated, the frontier charge
densities give the better correlations irrespective of the electrophile. The
results quoted relate to nitration in sulphuric acid, for which data were
widely available. However, this choice requires some justification since the
isomer ratios may change drastically with the conditions. In particular,
nitrations in acetic anhydride tend to give more ortho products [ 151. This is
a contentious issue, and while there is evidence [ 151 for a common electro-
phile in both acetic anhydride and sulphuric acid, it is generally held that
there is a greater interaction with the medium in the former case and that the
electrophile in sulphuric acid is more like the free NO,+ ion. These conditions
are therefore the most appropriate when attempting correlations with calcu-
lations on isolated molecules.
An attempt to correlate the rates of aromatic substitutions with frontier
orbital concepts must take into account both the charge at a position and
the energy of the appropriate orbitals. Fukui et al. have defined superdeloca-
lisability [17], S,, for an atom r in terms of orbital coefficients

s,= c c,? (6)

i E
(WC.)

For polycyclic hydrocarbons this gives good agreement with experimental

data over several powers of ten. By analogy, we define a frontier rate factor,
F’, for the sphere-charge case as

F = QHOMO + qNHOM0
(71
E HOMO ENHOMO
312

TABLE 3

Frontier rate factors

Position Partial Fr Overall l/N r. F,

rate factor relative rate atoms

1 1.0898 1 1.0898

o-42.0 1.1447
m-2.5 1.0771 24.4 1.1087
p-5.8 1.0998

CH2CHJ o-31.4 1.1843

m-2.3 1.0492 22.82 1.1109
p-69.5 1.0875

CH2Cl
o-O.72 1.0366
m-0.30 1.0246 0.71 1.0269
p-2.24 1.0119

NO2
o-2 x 10-a 0.7336
m-3 X lo-’ 0.7198 101 0.5815
p-3x lo* 0.0006

o-O.03 1.0513
m-0.001 0.9437 0.04 0.9762
p-o.14 0.8911

OCHJ
O-100 1.2878
m-l 0.9687 120 1.1097
p-400 1.0356

C6H5
O-41.0 1.1719
m-O.6 1.0714 24.24 1.1136
p-38.0 1.0816

In the case of biphenyl, four orbitals must be included (a pair of HOMOs

and a pair of NHOMOs) since there is essentially no interaction between the
two rings.
A comparison with available rate data [16], is given in Table 3. As might
be expected the detailed correlation is not very good, since we have ignored
such effects as steric hindrance and solvation energies. Nevertheless it is
possible to predict the relative overall reactivities of a series of compounds,
as illustrated in Fig. 4.
 313

Overall frontier rate factor

Fig. 4. Logarithm of overall relative rate vs. overall frontier rate factor for the nitration
of some aromatics.

CONCLUSIONS

Charges within spheres surrounding the carbon atoms in an aromatic

molecule may be calculated for any molecular orbital of interest. A weighted
mixture of the HOMO and NHOMO charges may be used with confidence to
predict the position of electrophilic substitution, particularly for more
complicated molecules.
The choice of radius for the spheres is somewhat arbitrary but since the
variation of charge with radius is approximately linear over the range of
chemical interest, it does not affect comparisons of a series of compounds.
The use of sphere charges is currently being applied to the chemistry of
heterocyclic compounds and to pericyclic reactions.

ACKNOWLEDGEMENTS

We should like to thank the S.R.C. for support of this work, and I.C.I. for
a CASE award (to V. S.).

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