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Volume 12 | Number 6 | 14 February 2010 | Pages 12051408

ISSN 1463-9076

COVER ARTICLE
Alonso and Herradn
Substituent effects on the aromaticity
of carbocyclic five-membered rings

PERSPECTIVE
Ashfold et al.
* excited states in molecular
photochemistry

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PAPER

www.rsc.org/pccp | Physical Chemistry Chemical Physics

Substituent eects on the aromaticity of carbocyclic ve-membered

ringsw
Mercedes Alonso* and Bernardo Herradon*

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Received 22nd August 2009, Accepted 25th September 2009

First published as an Advance Article on the web 21st October 2009
DOI: 10.1039/b917343a
The inuence of the substituent nature, as well as the number and position of the substituents,
on the aromaticity/antiaromaticity of a comprehensive set of derivatives of cyclopentadienyl anion,
cyclopentadiene and cyclopentadienyl cation has been analyzed. The aromaticity/antiaromaticity
of substituted cyclopentadienyl derivatives has been measured using energetic, magnetic and
structural criteria to take into account the multidimensional character of aromaticity.
Furthermore, the Euclidean distance values (dj) for all compounds have been estimated using
the neural network developed previously. It has been demonstrated that the dj as a scale of
aromaticity overcomes the particular limitations of the ASE, L, NICS and HOMA indices to
describe the changes in the aromaticity of cyclopentadiene ring due to substituent eects.
Additionally, it is shown that neural networks are useful tools for establishing structureproperty
relationships. The results indicate that mostly the aromaticity of cyclopentadiene ring and
cyclopentadienyl anion ring decrease upon substitution irrespective of the electronic character of
the substituent. The electron-donating groups, especially hydroxyl groups, destabilize carbanion
to a larger extent than electron-accepting ones. On the other hand, all the substituents reduce
strongly the antiaromaticity of the cyclopentadienyl cation. These results can be useful for the
design of new cationic ligands with lowered instability and new cyclopentadienyl ligands with
improved stability and reactivity.

Introduction
An important objective of modern Chemistry is to predict
behaviour that in turn helps to design useful materials.1
To achieve this goal, a deep structural knowledge is
necessary.2 Structureproperty relationships are key concepts
that are extremely useful to rationalize dierent chemical,
physical, biological and technological properties.3 Aromaticity
is a phenomenon exhibited by many organic compounds
and it relates energetic stabilization to cyclic p-electron
delocalization.47 Aromaticity refers to the existence of some
properties similar to those of benzene such as: energetic
stabilization; bond length equalization; a particular reactivity;
and characteristic spectroscopic and magnetic properties
related to strong, induced diamagnetic ring currents.810
Additionally, this concept has been used to justify or even
predict the stability and reactivity of inorganic compounds11
and has guided the design of new materials, such as spherical
Instituto de Qumica Organica General, C.S.I.C., Juan de la Cierva 3,
28006 Madrid, Spain. E-mail: mercuea@iqog.csic.es,
herradon@iqog.csic.es; Fax: 34 915644853; Tel: 34 915618806
w Electronic supplementary information (ESI) available: Fig. S1 and
Table S1 show the interrelation between NICSzz(1) values calculated at
the geometrical ring center and those evaluated at the ring critical
point; Fig. S2S4 display the bond lengths of the optimized geometries
of substituted cyclopentadienyl compounds; Fig. S5S7 show the
variation of the Euclidean distance values with the number and
position of substituents; Fig. S8S10 show the NICS scan proles of
some derivatives; Tables S2S4 include the Cartesian coordinates,
total energies and magnetic susceptibilities of all compounds. See
DOI: 10.1039/b917343a

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homoaromatic Si812 and all-metal clusters,13 which have been

found to possess aromaticity and antiaromaticity following
the Huckel rule. Although aromaticity is one of the most
widely used terms in Chemistry, it is a concept dicult
to dene unequivocally and, what is more important,
complicated to quantify.10,14 However, despite these drawbacks,
the concept is frequently used in a qualitative manner
and most organic compounds can be sorted out in three
broad groups: aromatic, non-aromatic and antiaromatic.15 A
thorough denition of aromaticity was given by Schleyer and
Krygowski.8,9
From a scientic point of view, each property has to be
measured. The fact that aromaticity is not an observable
hampers its quantication.16,17 Consequently, aromaticity
has to be gauged by convention and related to a reference,
usually benzene, the prototypical aromatic compound.
Aromaticity is manifested in a variety of ways: structural,18
energetic,19,20 magnetic,21,22 electronic23,24 and chemical
reactivity25 and each of these criteria has led to one or more
aromaticity descriptors.26,27 However, due to its dierent
physical manifestations, there is not a single indicator of
aromaticity that works properly for all cases.28,29 As a
consequence, it is necessary to use a set of indices based on
dierent physical properties to analyze aromaticity, as shown
by very recent studies.30 Although some attempts have been
done to gauge aromaticity through a linear combination of
several descriptors, the result is not satisfactory since the
mutual relationships between aromaticity indices depend
strongly on the choice of molecules in the sample.26,29,31 This
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divergence has led to much debate on the statistical multidimensionality of aromaticity;14,32 this issue is discussed below
and elsewhere.33
Recently, we have reported that articial neural networks
(ANNs) are useful tools to classify organic compounds into
aromatic/non-aromatic/antiaromatic.33 Besides the qualitative
ordering into the three groups, the self-organizing map
(SOM)34 is able to quantify the aromaticity of a comprehensive
set of ve-membered rings through the Euclidean distance
between neurons. Since several energetic and magnetic indices
of aromaticity have been used as molecular descriptors in the
neural network, the Euclidean distance is the rst scale
of aromaticity which takes into account these dierent
manifestations of the aromaticity.35 Unsupervised neural
networks like self-organizing maps are able to apprehend
complex and non-linear relationships between dierent
descriptors. This feature is important to apply the method to
a large variety of compounds, including those with dierent
substituents or dierent ring sizes. In a very recent article, we
have applied the SOM to establish a universal scale of global
aromaticity for p-organic compounds.36
The main objective of this research was to study systematically the inuence of the substituent on the aromaticity/
antiaromaticity of a large set of derivatives of cyclopentadienyl
anion (Cp), cyclopentadiene (Cp) and cyclopentadienyl
cation (Cp+) using self-organizing maps. To this end, we have
chosen four substituents (CH3, OH, F, CN) that cover the
main electronic eects such as electron-donating and withdrawing resonance eects, electron-donating and withdrawing
inductive eects as well as hyperconjugative eect (see Table 1
for the substituent constants).37,38 Additionally, we have
analyzed the eect of the number and position of the
substituent on aromaticity. The study of the substituent eect
on chemical properties is a long topic in physical organic
chemistry.39,40 However, only a few systematic studies on the
relation between the substituent eect and aromaticity have
been carried out, mostly on benzene derivatives.4143
Computational details

L = wM  wM 0

All calculations have been performed with Gaussian 03

package of programs at the MP2 level of theory with
the 6-311+G(d,p) basis set.44 The geometries of all
substituted cyclopentadienyl compounds 184 (Fig. 1) were
fully optimized and characterized by harmonic vibrational
Table 1

frequency computation. All structures corresponded to

minima on the potential energy surface, with no imaginary
frequencies.
As an energetic measure of aromaticity, we have used the
aromatic stabilization energy (ASE) which is the enhanced
stability of the aromatic compounds compared to their olenic
analogs.19,45 It is dened as the dierence between the energy
of a compound with cyclic p-electron delocalization and a
model reference system with (almost) no p-electron delocalization.
The strain-balanced homodesmotic reaction showed in
Scheme 1 was used to evaluate the ASE of substituted
cyclopentadienyl compounds. This equation is an adapted
version of the reaction used for calculating the ASE of vemembered heterocycles in a previous work.33 Homodesmotic
schemes based on cyclic reference compounds are strongly
recommended for ASE and other aromaticity evaluations
since they minimize additional eects such as topological
charge stabilization, hybridization, hyperconjugation,
etc.46,47 The energies were corrected by MP2/6-311+G(d,p)
zero-point energies. Systems with strongly positive ASEs are
aromatic, whereas those with strongly negative ASEs are
considered to be antiaromatic.
The magnetic susceptibility exaltation and the nucleus
independent chemical shift (NICS) have been used as magnetic
descriptors of aromaticity. Magnetic indices are based on the
p-electron ring current that is induced when the system
is exposed to external magnetic elds.21,22 The magnetic
susceptibility exaltation (L) is dened as the dierence
between the magnetic susceptibility of a compound (wM) and
a reference one without cyclic electron delocalization (wM0 )
[eqn (1)].48 The exaltations of substituted cyclopentadienyl
compounds were obtained from the reaction indicated in
Scheme 1. The magnetic susceptibilities were computed using
the CSGT method49 at the HF/6-311+G** level of theory.
The exaltations are negative (diamagnetic) for aromatic
compounds and positive (paramagnetic) for antiaromatic
compounds.

Substituent constants: s+, s, sm, sp, sR1, R+ and Ra

Substituent

s+/sb

smc

spc

sR1d

R+/Rd

OH
CH3
H
F
CN

0.92
0.31
0.00
0.03
1.00

0.12
0.06
0.00
0.34
0.56

0.37
0.17
0.00
0.06
0.91

0.40
0.10
0.00
0.34
0.09

1.25
0.32
0.00
0.52
0.49

a
Data were taken from ref. 43. b s+ and s are complex substituent
constants that contain both inductive and mesomeric eects for
electron-donating and electron-accepting substituents, respectively.
c
sm and sp are the Hammetts constants and are quantied from
the ionization constants of meta- or para-substituted benzoic acids.
Whereas sm is a eld inductive parameter, sp takes into account both
eects. d sR1, R+ and R are resonance parameters.

1306 | Phys. Chem. Chem. Phys., 2010, 12, 13051317

(1)

NICS is dened as the negative value of the absolute magnetic

shielding computed at ring centers or another interesting point
of the system.50,51 The NICS(1) values calculated 1 A above
the molecular plane are considered to better reect the
p-eects. Another descriptor is the out of plane component
of the tensor NICS computed at 1 A above the ring center,
denoted as NICSzz(1), which was recently found to be a good
measure for the characterization of the p system of the ring.52
The GIAO/HF/6-311+G(d,p) method was used for the NICS
calculations.53 Rings with highly negative values of NICS are
quantied as aromatic, whereas those with positive values are
antiaromatic. In contrast to ASE and L, NICS is an absolute
measure of aromaticity in the sense that its evaluation does not
require the use of reference compounds. Recently, the NICS
values as a function of the distance (NICS scan) have been
proposed as an aromaticity criterion.54 For aromatic systems
the NICS scan passes through a minimum, while for antiaromatic species no minimum is observed. In order to check
the inuence of the ring center coordinates on the NICS
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Scheme 1 Homodesmotic reactions used to evaluate the aromatic stabilization energies (ASE) and magnetic susceptibility exaltation (L) of
substituted cyclopentadienyl compounds.

values, the NICS values of 20 substituted cyclopentadienyl

compounds have been also evaluated in the ring critical point
(rcp),55 as suggested by Morao and Cossio.56 The results at
the rcp are practically identical to those calculated at the
geometrical ring center and they are reported in the ESI
(Table S1 and Fig. S1).w
As a structure-based measure, we have employed the
harmonic oscillator model of aromaticity (HOMA) dened
by Kruszewski and Krygowski as,57
HOMA 1 

n
aX
Ropt  Ri 2
n i1

Where n is the number of bonds taken into the summation,

and a is an empirical constant xed to give HOMA = 0 for a
model non-aromatic system and HOMA = 1 for a system
with all bonds equal to an optimal value Ropt, assumed to be
realized for fully aromatic systems. Ri is the running bond
length. This index has been found to be one of the most
eective structural indicators of aromaticity.18
The aromaticity indices were used as molecular descriptors
for the substituted cyclopentadienyl compounds in the
Kohonen network developed previously with the SOM_PAK
program.58,59 The theoretical background of SOMs is
explained in detail elsewhere.33 The Euclidean distance dj
between the input vector Xp (xp1, xp2,. . .,xpm) and the weights
of the winner neuron Wj (xj1, xj2,. . .,xjm) were calculated
according to eqn (3).
dj

m
X

xpi  wji 2

i1

According to the neural network, the Euclidean distance

ranges from 0 to 33.2 for aromatic systems, from 35.3 to

68.3 for non-aromatic compounds and from 72.6 to 170.6 for

antiaromatic molecules. For the most aromatic system (benzene),
dj is 0 and the higher dj the less-aromatic the ring.36

Results and discussion

Substituted cyclopentadienyl anions
Cyclopentadienyls have been among the most important
ligands in organo-transition metal chemistry because they
form a wide range of stable complexes whose steric and
electronic properties can easily be tailored by varying the ring
substituents.60 Interest in modifying transition metal complexes
using substituted cyclopentadienyl rings has been stimulated in
recent years by their potential synthetic and catalytic applications
in dierent processes. The inuence of dierent substituents
in the cyclopentadienyl ring on the chemical behaviour of
compounds of this type has been widely studied. Replacement
of one or more of the cyclopentadienyl ring hydrogen atoms
with various dierent substituents has resulted in signicant
changes in reactivity, stability, catalytic activity and other
properties.61 However, to our knowledge, the substituent
eect on the aromaticity of Cp has not been previously
reported.62
The cyclopentadienyl anion (Cp) has a conjugated six
p-electron system and hence fulls the Huckel (4n + 2) rule.
The large energetic stabilization, the equalized bond lengths,
the highly negative values of NICS indices and the fully cyclic
delocalized p-electron system, assessed by several electronic
indices, conrms its considerable aromatic character.30
Accordingly, SOM places Cp in the region of the highly
aromatic compounds with dj = 13.1 related to benzene
(dj = 0.0). Table 2 collects the aromaticity descriptors of all

Fig. 1 Substituted cyclopentadienyl compounds included in the study of the substituent eect.

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substituted cyclopentadienyl anions: aromatic stabilization

energy (ASE), the magnetic susceptibility exaltation (L), the
isotropic NICS values computed at the ring center [NICS] and
at 1 A above the molecular plane [NICS(1)], the out-of-plane
component of the NICS tensor computed at 1 A above the
ring center [NICSzz(1)] and the harmonic oscillator model of
aromaticity (HOMA). The Euclidean distance values (dj) for
all the derivatives are also included.
As observed in Table 2, the dierent aromaticity descriptors
give contradictory results. This fact is indicative of the multidimensional character of aromaticity and the drawbacks of the
single indicators of aromaticity, justifying the necessity to use
appropriate algorithms, such as ANNs, to apprehend it. On
the one hand, the mean values of ASE, L and NICSzz(1)
indicate that the aromaticity of Cp ring decreases slightly
upon substitution irrespective of the electron-donating or
electron-accepting character of the substituent. According to
these descriptors, the aromaticity of the Cp ring decreases
linearly with the number of substituents, the tetrasubstituted
derivatives being the least aromatic in each series (Fig. S5w).
On the other hand, isotropic NICS values show an opposite

trend, indicating an increase of the aromaticity of Cp ring

with the number of hydroxyl groups, uorine atoms and cyano
groups. As previously reported, NICS, and to a lesser extent
NICS(1), contain large inuences from the s system and from
all three principal components of the NICS tensor.26,52,63
Similarly, HOMA fails to describe the loss of aromaticity in
the hydroxy- and uoro-derivatives as compared with the
unsubstituted Cp. HOMA values are quite dependent on
the parameter Ropt, which has been obtained from neutral
molecules. Moreover, it has been reported that HOMA fails in
some cases when the geometry is forced by s-electron
structure, such as cyclooctatetraene or some localized benzene
derivatives.64 Shishkin et al. showed that the structural
aromaticity indices are not able to reproduce the relatively
small changes in the aromaticity of the benzene ring due to the
substituent eect.65 For the substituted cyclopentadienyl
anions containing OH and F, HOMA increases signicantly
with the number of substituents.
The correlation coecients between the energetic, magnetic
and structural indices of aromaticity for all the substituted
derivatives of Cp are shown in Table 3. Although all

Table 2 Calculated ASE (kcal mol1), L (ppm cgs), NICS, NICS(1) and NICSzz(1) (ppm), HOMA and dj for substituted cyclopentadienyl anions
Erela

N1
C5H5

Cp

22,32,52,3,42,3,52,3,4,5Mean
Esd.

1
2
3
4
5
6

22,32,52,3,42,3,52,3,4,5Mean
Esd.

7
8
9
10
11
12

22,32,52,3,42,3,52,3,4,5Mean
Esd.

13
14
15
16
17
18

22,32,52,3,42,3,52,3,4,5Mean
Esd.

19
20
21
22
23
24

0.00
0.67
0.00
0.56

0.00
0.51
0.00
0.09

2.96
0.00
2.38
0.00

1.45
0.00
0.80
0.00

ASE

NICS

NICS(1)

NICSzz(1)

HOMA

dj

22.05

10.13

10.25

35.98

0.740

13.1

7.66
4.07
5.42
0.50
3.73
1.01
4.36
3.86

13.99
CH3
13.12
13.15
12.30
12.86
12.31
12.71
12.92
0.58

20.32
18.57
18.60
16.80
16.88
15.03
18.32
2.35

9.66
9.80
9.05
9.62
9.28
9.59
9.61
0.38

32.54
32.03
29.56
30.17
28.63
28.68
31.08
2.65

0.736
0.732
0.731
0.724
0.726
0.715
0.729
0.008

14.3
18.1
16.4
21.0
18.9
22.9
17.8
3.5

16.53
14.06
13.77
11.33
10.37
3.00
13.01
5.86

7.78
6.70
6.10
3.53
3.96
3.27
5.93
2.53

OH
15.33
17.71
16.95
19.98
18.96
20.23
17.59
2.35

9.64
9.89
9.13
10.05
9.34
10.44
9.82
0.48

32.35
30.77
29.09
29.08
27.08
22.88
29.60
4.12

0.760
0.786
0.773
0.793
0.803
0.820
0.782
0.027

17.8
20.1
20.5
24.2
25.6
33.1
22.1
6.4

18.46
17.49
15.26
16.59
13.57
11.31
16.39
3.48

8.58
7.19
7.23
4.56
5.62
4.22
6.79
2.15

F
16.69
20.25
19.66
23.80
22.98
26.68
20.58
4.34

10.00
10.55
9.90
11.17
10.53
11.86
10.61
0.69

32.92
31.90
30.29
30.93
29.12
29.24
19.96
2.27

0.776
0.827
0.799
0.848
0.855
0.890
0.819
0.051

15.5
17.2
19.4
19.3
20.7
24.2
18.5
3.6

25.82
19.61
26.66
9.15
18.94
8.83
17.26
6.92

7.47
7.53
6.09
8.16
6.68
7.81
7.83
1.13

CN
14.58
15.49
15.35
16.45
16.25
17.30
15.48
0.99

10.48
10.88
10.62
11.10
10.89
11.28
10.75
0.31

14.38
12.76
11.93
29.81
29.07
28.54
31.10
2.14

0.733
0.735
0.736
0.724
0.745
0.729
0.735
0.006

10.3
15.7
9.9
24.8
16.3
25.3
16.5
6.3

Erel is the relative energies (in kcal mol1) for the position isomers.

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Table 3 Correlation coecients between several descriptors of

aromaticity for substituted cyclopentadienyl anions

ASE
L
NICS
NICS(1)
NICSzz(1)
HOMA
dj

NICS

NICS(1) NICSzz(1) HOMA dj

ASE

1
0.292
0.476b
0.124
0.726a
0.406b
0.977a

1
0.009
1
0.254
0.588a 1
a
0.555 0.292 0.013
0.053 0.943a 0.370
0.466b 0.428b 0.096

1
0.245
0.781a

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Correlation is signicant at the 0.01 level (2-tailed).

signicant at the 0.05 level (2-tailed).

1
0.366
b

Correlation is

compounds are closely related structurally, poor mutual

correlations were found indicating that the dierent descriptors
are not statistically equivalent and it is necessary to use all of
them to characterize the cyclopentadienyl ligands properly.66
ASE, L, NICSzz(1) and HOMA are the indices with higher
correlations, being the most suitable among those examined in
this work for describing the changes of aromaticity of the Cp
ring due to the substituent eect. It is noteworthy that the
correlation between isotropic NICS values and the out-ofplane component is less than 0.3 and has a minus sign.
Using ASE, L, NICSzz(1) and HOMA as molecular
descriptors, we have applied the neural network to classify
the Cp derivatives according to their aromatic character. The
position of derivatives 124 on the two-dimensional map is
shown in Fig. 2. All substituted cyclopentadienyl anions are
classied as aromatic compounds with dj values (relative to
benzene) ranging from 9.9 to 33.1 (dj column in Table 2). The
large variation of dj indicates a great sensitivity of the
p-electron structure of the Cp ring to the substituent
eect. Except for cyano derivatives 19 and 21, all the
substituted cyclopentadienyl anions are less aromatic than
the unsubstituted Cp according to dj. Moreover, the variation
of the aromaticity depends on the nature of the substituent.
The mean of dj indicates that the OH substituent leads to the
largest loss of aromaticity of the Cp ring, followed by F,
CH3 and, nally, CN. The electron-accepting substituents
destabilize carbanion Cp to a lesser extent than electrondonating groups. In fact, the order provided by dj is related to
the resonance constants sR1, R+ and R.37 Therefore, the
resonance eects are more important than inductive eects in
the interaction between the substituent and the p-electron
cloud of the Cp.
Regarding to the relation between the position of the
substituent and the aromaticity of Cp, dj indicates that the
replacement of an H atom by CH3 or CN at position 3- and
4- leads to the largest decrease of aromaticity, so the 2,5disubstituted and the 2,3,5-trisubstituted species are more
aromatic than their respective regioisomers (Fig. S5w). For
OH and F, the opposite variation of aromaticity with the
position of the substituent is observed. These generalizations
are supported by ASE, HOMA and, in some series, by NICS
values. Interestingly, the order of stability is reversed with
regard to the order of aromaticity in the methyl- and uoroderivatives. The stability of the dierent position isomers
(Erel in Table 2) in these series of compounds does not seem
to be controlled by aromaticity but other factors. In contrast,
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for the substituents with strong resonance eects (OH and

CN), the most stable isomer is the most aromatic one and
vice versa. The relation between stability and aromaticity for
certain series of monocycles position isomers has been recently
discussed by Mandado et al.67 The fact that the most stable
isomer is not necessarily the most aromatic was previously
discussed by Havenith et al.68
The dierences in dj among the isomers become accentuated
for cyano derivatives due to the large variation of the ASEs of
these analogous compounds. The highly positive values of the
substituent constants indicates that the cyano group is a
strong electron-withdrawing substituent by both inductive
and resonance eects (s = 1.00, sp = 0.91 and sm = 0.56).
On one hand, the increase of aromaticity in the derivatives 19
and 21 could be explained by the increased stability caused
by the better accommodation of the negative charge. The
molecular orbitals of compound 21 (Fig. 3) prove the large
delocalization of the negative charge induced by the CN
groups at positions 2- and 5-. On the other hand, the loss of
aromaticity in the tri- and tetra-cyano species would be
justied by the decrease of p-electron density due to the strong
electron-withdrawing character of CN substituent as well
as steric hindrance caused by crowded substitution. It is
remarkable that the rest of the aromaticity descriptors
(L, HOMA and NICS) do not support a large variation of
aromaticity among the cyano isomers, suggesting that the
stabilization energies could be perturbed by additional eects.
Vianello et al. reported that the penta-cyanocyclopentadiene is an organic superacid due to a strong anionic
resonance eect in the resultant conjugate base which
outweighs the loss of aromaticity of Cp ring. They concluded
that aromatization as well as cationic and anionic resonance in
the corresponding conjugate acids and bases are the key
concepts in designing neutral organic superbases and superacids.69
Except for derivatives 1921 whose dj is B10, all derivatives
have a dj values bigger than 13.1, value corresponding to the
unsubstituted Cp. The use of a non-linear combination of
several aromaticity descriptors is better than a single indicator
of aromaticity to characterize the p-electron systems in organic
compounds, since dj is less sensitive to the particular failures of
ASE, L, NICS and HOMA.
The NICS scan of Cp, the tetrasubstituted species 6, 12, 18
and 24 and the 2,5-dicyano derivative 21 have been calculated
in order to analyze the substituent eect in the aromaticity of
the ring. The method consists of scanning the NICS values up
to a certain distance from the ring center for assessment of
aromaticity of organic and inorganic compounds.54 The NICS
scan is reported to be more reliable than single NICS values
and the scan shape can satisfactorily explain the aromatic/
antiaromatic behaviour in a particular system. Fig. 4 shows
the superposition of the out-of-plane curves and in-plane
curves of the substituted derivatives of Cp analyzed. All
the NICS scan plots show minima for the out-of-plane
component, indicating the presence of diamagnetic ring
currents in all the substituted cyclopentadienyl anions.
However, the magnitude of the minima changes for the
dierent derivatives. For Cp, the minimum value of the
out-of-plane component is 36.3 ppm, more negative than
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Fig. 2 Self-organizing map obtained for the classication of p-organic compounds according to their degree of aromaticity. Neurons are coloured
based on the Euclidean distance between the weight vector of each neuron and the neuron activated by benzene. Substituted cyclopentadienyl
anions and cyclopentadienes are indicated by the position of the substituent in the ring and the substituent. As comparative purposes, some
heterocycles used in the network training and benzene are shown.

Fig. 3 HOMOs of dicyano derivatives 20 and 21.

that of benzene itself (31.3 ppm) and appears at r = 1.0 A.

The magnitude of NICSzz decreases around 13.5 ppm from
Cp to the tetrahydroxy derivative 12, indicating a smaller
diamagnetic ring current in the latter. The minimal values of
the out-of-plane components become progressively less negative
in the order: Cp 4 21 (CN) E24 (CN) 4 18 (F) 4
6 (CH3) c12 (OH), suggesting that the diatropic ring current
of Cp decreases signicantly in the presence of substituents,
especially strongly electron-donating substituents like OH.
Unlike uncharged aromatic systems, such as benzene, the
in-plane component of Cp shows a paratropic maximum
due to the negative charge. This maximum is attened and
appears at larger distances from the molecular plane due to
the substituent eect, suggesting a decrease of the paramagnetic contribution to the in-plane component in
1310 | Phys. Chem. Chem. Phys., 2010, 12, 13051317

the order: H 4 CH3 4 F 4 OH 44 CN. In fact, the

paratropic maximum disappears in compound 24, proving the
large negative charge delocalization induced by the four cyano
groups.
Substituted neutral cyclopentadienes
Cyclopentadiene (Cp) and its derivatives are well known
compounds mainly used as dienes in DielsAlder reactions
and as sources for cyclopentadienyl anions.70 Cp not only
possesses the reactive conjugated double-bond structure but
also contains an active methylene group. As a consequence, a
large number of polymers and derivatives have been prepared
from cyclopentadiene with applications in the eld of synthetic
resins.71 Cp is a rather acidic hydrocarbon (pKa E 16) due to
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Fig. 4 Superposition of the NICSzz-scan proles (a) and

NICSxx/yy-scan proles (b) of some substituted cyclopentadienyl
anions and benzene.

the aromatic character of its corresponding anion.72 The

possible aromaticity of Cp through the 2p hyperconjugative
of the methylene group has been long discussed.20,73,74
However, Cp does not follow Huckels rule and consequently
it is classied as non-aromatic compound by the neural
network with a dj = 41.5 in conformity with a recent
analysis.74 Furthermore, Cp exhibits bond alternation unlike
aromatic systems. The presence of a small diamagnetic ring
current in Cp, as demonstrated by the chemical shifts of the
protons
and several magnetic indices, is not a sucient condition for
aromaticity. This phenomenon is named hyperconjugation.75
The energetic, magnetic and structural descriptors of
aromaticity as well as the dj values of all substituted cyclopentadienes are collected in Table 4. The relative energies of
position isomers in the series are also included. All the
substituents reduce the p electronic delocalization of Cp ring
irrespective of their electron-donating or accepting nature. As
substitution increases, Cp is energetically destabilized, L and
NICSzz(1) increases and the bond alternation increases as
indicated by HOMA. On the contrary, isotropic NICS values
give an opposite trend for hydroxy-, uoro- and cyanoderivatives indicating an increase of aromaticity of Cp ring
with these substituents. According to NICS, several substituted
cyclopentadienes (X = OH, F) are more aromatic than
benzene itself (NICS = 9.55 ppm). Similarly, HOMA fails
to describe the aromaticity of the cyano cyclopentadienes since
it erroneously points out that the derivatives 5260 are more
aromatic than Cp.
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For substituted cyclopentadienes, the correlation coecients

between dierent aromaticity indices are far away from 1
(Table 5), suggesting that it is necessary to use all of them to
describe the substituent eect on the aromaticity of Cp ring.
Again, the dierent parameters provide a distinct order of
aromaticity for the substituted cyclopentadienes, being
necessary a scale of aromaticity as dj which takes into account
the dierent aspects of this phenomenon.
Despite the particular limitations of HOMA, dj is able to
point out the loss of aromaticity for all functionalized cyclopentadienes as compared with the unsubstituted Cp. All the
substituted cyclopentadienes are placed in the region of the
non-aromatic compounds with dj ranging from 41.5 to 53.7,
being the tri- and tetra-substituted derivatives the least
aromatic in each series. According to the mean values of dj,
uorine leads to the maximum reduction of the aromaticity
of Cp ring, followed by OH, CN and CH3. It is noteworthy that L, NICSzz(1) and HOMA give a dierent
aromaticity order.
Regarding the relation between the substituent position
and the aromaticity of Cp ring (Fig. S6w), the species 2,5disubstituted and 2,3,5-trisubstituted with electron-donating
groups (X = CH3, OH) are less aromatic than their respective
regioisomers and they are classied as the least aromatic
species in these series. In the uoro- and cyano-derivatives,
the 2,3,4,5-tetrasubstituted systems are the least aromatic
species. In contrast to the rest of substituents, the aromaticity
of 2,5-dicyano systems is substantially higher than that of their
3,4-isomers. For substituted cyclopentadienes, the relative
energies of the position isomers follow the same trend as the
aromaticity of Cp ring, so the relative energy increases as the
aromaticity of the Cp ring decreases.
The NICS scans of Cp and substituted cyclopentadienes 33,
39, 41, 51 and 60 have been calculated in order to explain the
aromaticity changes due to the substituent eect in Cp. The
superposition of the out-of-plane and in-plane curves of these
functionalized cyclopentadienes is showed in Fig. 5. For all the
derivatives, the out-of-plane component shows a shallow
minimum suggesting the presence of a small diamagnetic
current in all substituted cyclopentadienes. However, the
minimum values of the out-of-plane component decreases
signicantly in presence of substituents compared to that of
Cp in the following order: Cp 4 33 (X = CH3) 4 51 (X = F) 4
39 (X = OH) 4 60 (X = CN). There is an enhancement of the
paramagnetic contribution to the out-of-plane component due
to the substituent so the diamagnetic current is smaller in the
substituted cyclopentadienes. Interestingly, none of the derivatives show a typical antiaromatic NICS scan curve characterized by a steady decrease in chemical shift with no
minimum.
As reported by Stanger,54 the general shape of the isotropic
curves are governed by the out-of-plane component in
aromatic and antiaromatic systems and about equally by the
in-plane and out-of-plane components in the non-aromatic
molecules. In Fig. S9,w it is observed that the in-plane
contribution to the NICS values increases signicantly with
the electronegativity of the substituents, explaining why the
isotropic NICS values can not be used as a reliable aromaticity
index for uoro-, hydroxy- and cyano-cyclopentadienes.
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Table 4

Calculated ASE (kcal mol1), L (ppm cgs), NICS, NICS(1) and NICSzz(1) (ppm), HOMA and dj for substituted cyclopentadienes

CH3

N1

C5H6

Cp

232,32,43,42,52,3,42,3,52,3,4,5Mean
Esd

25
26
27
28
29
30
31
32
33

232,32,43,42,52,3,42,3,52,3,4,5Mean
Esd

Erela

ASE

NICS

HOMA

dj

4.82

11.83

0.778

41.5

1.12
0.71
1.58
1.62
0.73
2.25
1.54
2.66
2.58
1.48
0.86

4.03
4.79
4.12
3.99
4.84
3.37
4.19
3.41
3.57
4.11
0.56

8.86
10.78
8.14
7.86
10.15
5.32
7.60
5.42
5.06
8.10
2.37

0.789
0.820
0.875
0.885
0.848
0.912
0.904
0.903
0.957
0.867
0.057

43.4
42.0
44.1
44.1
42.3
46.4
44.5
46.4
46.4
44.1
1.9

1.96
1.31
3.51
2.60
2.16
6.75
2.96
7.93
6.45
3.56
2.61

1.09
0.55
1.41
0.90
0.64
1.85
0.12
1.89
1.36
0.85
0.83

OH
3.35
5.51
6.20
6.05
8.57
4.31
9.74
7.10
10.86
6.49
2.61

3.45
4.84
4.14
3.67
5.31
2.57
4.62
3.25
4.57
4.12
0.86

6.87
10.34
6.87
6.11
10.22
2.86
6.87
3.06
4.14
6.92
3.10

0.776
0.801
0.754
0.797
0.889
0.912
0.807
0.910
0.853
0.828
0.059

45.2
42.7
46.3
46.3
43.5
51.2
45.7
52.4
50.5
46.7
3.5

1.20
0.00
4.39
0.00
1.37
2.11
0.16
0.00

2.47
1.27
3.73
3.77
5.14
5.88
7.67
7.51
11.73
4.92
3.46

0.85
0.26
0.87
0.03
0.27
0.81
0.32
0.41
0.24
0.34
0.46

F
4.31
6.35
8.25
7.93
10.03
6.25
12.17
10.15
14.28
8.29
3.45

3.88
4.92
4.54
4.24
5.37
3.37
5.14
4.12
5.07
4.55
0.63

7.62
10.65
7.53
7.30
10.44
4.44
7.83
4.61
5.28
7.75
2.57

0.764
0.798
0.714
0.789
0.889
0.816
0.809
0.765
0.800
0.783
0.059

45.2
42.7
46.0
46.0
45.7
50.0
49.5
50.7
53.7
47.1
3.8

0.00
1.37
1.74
2.00
3.55
0.00
1.76
0.00

0.16
1.22
0.76
3.67
5.21
1.67
6.64
4.88
9.43
3.33
3.18

0.27
0.48
0.21
0.39
0.80
0.25
0.45
0.31
0.27
0.34
0.21

CN
4.15
4.25
5.16
5.17
5.16
5.08
6.05
6.03
6.84
5.11
1.06

5.22
5.13
5.44
5.41
5.32
5.50
5.57
5.63
5.77
5.38
0.27

11.15
11.31
10.69
10.43
10.64
10.40
9.94
9.82
9.21
10.54
0.77

0.713
0.754
0.691
0.706
0.732
0.649
0.687
0.646
0.660
0.702
0.044

41.6
42.2
42.1
45.0
45.7
43.2
47.9
45.9
49.7
44.7
2.7

0.00

0.25
0.00
0.95
0.59
0.00
0.92
0.00
0.65

0.73
0.48
0.97
1.09
0.50
1.41
1.11
1.76
1.66
0.97
0.56

34
35
36
37
38
39
40
41
42

0.64
0.00
3.91
0.44
0.00
4.60
0.00
4.97

232,32,43,42,52,3,42,3,52,3,4,5Mean
Esd

43
44
45
46
47
48
49
50
51

232,32,43,42,52,3,42,3,52,3,4,5Mean
Esd

52
53
54
55
56
57
58
59
60

Erel is the relative energies (in kcal mol1) for the position isomers.

Table 5

Correlation coecients between several descriptors of aromaticity for substituted cyclopentadienes

ASE
L
NICS
NICS(1)
NICSzz(1)
HOMA
dj
a

NICSzz(1)

3.18
CH3
2.17
3.03
2.16
2.00
2.95
1.17
2.09
1.34
1.27
2.14
0.74

0.00

NICS(1)

ASE

NICS

NICS(1)

NICSzz(1)

HOMA

dj

1
0.173
0.725a
0.067
0.464a
0.109
0.416b

1
0.616a
0.750a
0.576a
0.540a
0.306a

1
0.347b
0.167
0.191
0.502a

1
0.784a
0.640a
0.100

1
0.511a
0.188

1
0.060

Correlation is signicant at the 0.01 level (2-tailed).

Correlation is signicant at the 0.05 level (2-tailed).

1312 | Phys. Chem. Chem. Phys., 2010, 12, 13051317

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Fig. 5 Superposition of the NICSzz-scan proles (a) and NICSxx/yy-scan

proles (b) of the substituted cyclopentadienes analyzed.

Substituted cyclopentadienyl cations

The cyclopentadienyl cation (Cp+) is very important in
the study of diradicals as well as in the understanding of
antiaromaticity and its eects on structure and chemical
reactivity.76 Cp+ is predicted to be involved as an intermediate
in the rst steps of soot formation and in the oxidation of
aromatic hydrocarbons.77 Experimentally, it has been detected
by mass spectrometry and photoelectron spectroscopy.78,79
Moreover, several ab initio calculations on the electronic states
of Cp+ and its antiaromaticity have been published.80
However, a systematic study of the substituent eect on the
antiaromaticity of Cp+ has not been previously reported.
According to Huckels rule, Cp+ with four p electrons is
antiaromatic. Its antiaromatic character has been assessed by
several energetic, magnetic, electronic and structural descriptors
of aromaticity.20,30,50 In fact, singlet Cp+ is mapped into the
neuron which represents the highest degree of antiaromaticity
(lowest degree of aromaticity), being the most antiaromatic
ve-membered ring of the comprehensive dataset used in the
training and validation of the network.
Table 6 encloses the corresponding ASE, L, NICS,
NICS(1), NICSzz(1) and HOMA for the dierent substituted
cyclopentadienyl cations. All indices point out that the substituents, irrespective of their nature, decrease the antiaromaticity
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of Cp+ signicantly. Except HOMA, the dierent aromaticity

descriptors indicate that hydroxyl group is the substituent
which leads to the largest loss of antiaromaticity, followed
by F, CH3 and, nally, CN. Electron-donating substituents
stabilize Cp+ to a large extent than electron-accepting ones
due to the delocalization of the positive charge, contrarily to
Cp. For substituted cyclopentadienyl cations, all descriptors
of aromaticity exhibit better mutual correlations (Table 7)
than those of neutral and anionic cyclopentadienes. The
correlations between the exaltation and the NICS-based
indices are excellent, indicating that both describe a similar
trend for the antiaromaticity changes induced by the substituent in Cp+. Good correlations exist between indices based
on dierent physicochemical properties such us ASE vs.
NICSzz(1) and HOMA vs. NICS. The isotropic NICS values
can be used as a reliable descriptor of the degree of antiaromaticity in the Cp+ ring, although they do not describe
correctly the aromatic/non-aromatic character for most of
the derivatives of Cp and Cp.
The dj values for all substituted derivatives of Cp+ are
included in Table 6. According to the neural network antiaromatic compounds possess dj values ranging from 72.6 to
170.6 and the smaller value of dj, the less antiaromatic is the
compound. The large decrease in dj indicates that Cp+ is
strongly stabilized by the substituents, especially the electrondonating ones. The degree of antiaromaticity of Cp+ ring is
determined by the number and position of the substituents as
well as its nature. Except for cyano-substituted Cp+, the
2,5-disubstituted derivatives have the lowest antiaromaticity,
followed by 2,3,5-trisubstituted species (Fig. S7w). The
replacement of an H atom by substituent at position 2- induces
a decrease of antiaromaticity signicantly larger than the
replacement at position 3-. Furthermore, the relative energies
indicate that the 2,5-disubstituted and 2,3,5-trisubstituted
species are the most stable compounds among the isomer
positions. The largest positive charge delocalization is found
in these derivatives as indicated by the CC distances of the
optimized geometries (Fig. S4w). For the cyano cyclopentadienyl
cations, the dierences in dj between the position isomers are
small, being the 2,5-disubstituted and the 2,3,5-trisubstituted
derivatives the most antiaromatic in this series. According to
the mean and the standard deviation of dj, the cyano group is
the substituent that induces the smallest loss of antiaromaticity
of Cp+ ring because it destabilizes cation by inductive eect.
The antiaromaticity order provided by dj (CN 4 CH3 4 F 4
OH) is in agreement with the rest of descriptors, except
HOMA. All substituted cyclopentadienyl cations are classied
as antiaromatic with dj between 72.6 and 167.8. Interestingly,
the hydroxy derivatives 180 and 182 are placed in the neurons
nearest to the non-aromatic cluster. These results can serve as
a guide for the design of new cationic ligands to bind anions in
material science or catalysis. Additionally, they open new
perspectives on putative transient species in organic reactions.
Fig. 6 shows the superposition of the out-of-plane curves
and in-plane curves of some substituted cyclopentadienyl
cations. The isotropic NICS scan of the parent Cp+ behaves
like that of an antiaromatic system: the large paramagnetic
contribution leads to a steady decrease in chemical shift with
no minimum. The values of NICS are highly positive and the
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Table 6 Calculated ASE (kcal mol1), L (ppm cgs), NICS, NICS(1) and NICSzz(1) (ppm), HOMA and dj for substituted cyclopentadienyl cations
Erela

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C5H5

Cp

22,32,52,3,42,3,52,3,4,5Mean
Esd

61
62
63
64
65
66

22,32,52,3,42,3,52,3,4,5Mean
Esd

67
68
69
70
71
72

22,32,52,3,42,3,52,3,4,5Mean
Esd

73
74
75
76
77
78

22,32,52,3,42,3,52,3,4,5Mean
Esd

79
80
81
82
83
84

14.0
0.0
26.9
0.0

13.2
0.0
12.4
0.0

4.0
0.0
3.8
0.0

NICS

NICS(1)

NICSzz(1)

HOMA

dj

57.88

35.54

44.78
50.56
36.50
51.47
40.83
48.27
47.18
7.14

21.16
25.43
14.46
17.85
16.27
18.63
21.33
7.20

51.32
CH3
34.00
39.32
27.87
30.58
29.33
32.27
34.96
8.12

35.57

112.21

1.152

170.6

21.04
25.59
15.77
17.95
16.98
19.20
21.73
6.90

69.10
83.56
54.57
63.22
58.56
67.24
72.64
19.75

0.982
1.454
1.047
1.083
1.207
1.089
1.145
0.154

131.1
146.5
113.2
132.3
122.7
132.2
135.5
18.5

22.74
39.39
1.76
65.40
12.29
36.57
33.72
23.20

13.61
17.50
7.86
20.30
7.87
11.26
16.28
9.68

OH
20.85
24.21
13.20
24.95
10.66
11.78
22.42
14.05

11.77
16.02
7.31
18.59
6.77
9.35
15.05
10.05

40.95
54.47
28.57
63.67
28.03
38.05
52.28
29.46

0.824
0.720
0.694
0.893
0.544
0.491
0.760
0.224

99.6
116.1
72.6
137.5
78.0
101.7
110.9
34.3

36.99
48.25
22.64
54.36
29.22
43.15
41.78
12.96

19.96
22.94
14.47
21.17
14.37
16.88
20.76
7.30

F
29.86
39.32
21.78
24.57
18.36
17.85
29.01
12.35

19.02
25.59
14.22
18.73
13.18
14.70
20.14
8.00

62.45
83.56
48.55
64.19
46.50
53.09
67.22
23.45

0.952
1.073
0.778
0.846
0.852
0.838
0.927
0.138

122.7
146.5
101.4
134.4
103.3
116.1
127.9
24.8

52.38
53.51
44.52
46.28
40.12
44.62
48.47
6.25

32.69
31.42
29.73
29.01
28.06
29.63
30.87
2.57

CN
47.44
45.68
41.78
41.48
38.84
42.02
44.08
4.28

32.93
32.16
28.79
29.34
27.22
30.51
30.93
2.83

104.78
104.61
92.50
96.34
88.78
101.09
100.05
8.06

1.129
0.879
0.971
0.920
1.093
0.889
1.005
0.117

167.8
167.8
153.8
156.1
149.7
160.6
160.9
8.0

Erel is the relative energies (in kcal mol1) for the regioisomers.

Table 7

Correlation coecients between several descriptors of aromaticity for substituted cyclopentadienyl cations

ASE
L
NICS
NICS(1)
NICSzz(1)
HOMA
dj
a

7.3
0.0
3.7
0.0

ASE

ASE

NICS

NICS(1)

NICSzz(1)

HOMA

dj

1
0.719a
0.600a
0.681a
0.685a
0.377
0.694a

1
0.956a
0.992a
0.989a
0.576a
0.939a

1
0.980a
0.975a
0.694a
0.908a

1
0.998a
0.607a
0.941a

1
0.599a
0.948a

1
0.510a

Correlation is signicant at the 0.01 level (2-tailed).

Correlation is signicant at the 0.05 level (2-tailed).

out-of-plane curve presents a maximum at 0.4 A of 160 ppm.

Unlike the uncharged antiaromatic compounds, the in-plane
component shows a minimum due to the positive charge. The
isotropic NICS curve is governed mainly by the out-of-plane
component. Substitution reduces drastically the paramagnetic
contribution to the out-of-plane component. For the substituted
derivatives, the maximum value of the out-of-plane curve
shifts slightly left to smaller distances compared to the
1314 | Phys. Chem. Chem. Phys., 2010, 12, 13051317

unsubstituted Cp+ and decrease signicantly in the order:

Cp+ 4 83 (X = CN) 4 65 (X = CH3) 4 75 (X = F) 4
69 (X = OH). Therefore, the paramagnetic ring current of
Cp+ is reduced remarkably by substituents, especially strong
electron-donating groups like OH. In 69, the minimum for the
in-plane component disappears proving the great delocalization
of positive charge induced by the hydroxyl groups at positions
2- and 5-.
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Fig. 6 Superposition of the NICSzz-scan proles (a) and NICSxx/yy-scan

proles (b) of the substituted cyclopentadienyl cations analyzed.

irrespective of the substituent nature. The electron-accepting

substituents destabilize carbanion Cp to a lesser extent than
electron-donating groups. In particular, the negative charge is
strongly stabilized in cyano cyclopentadienyl anions. The
aromaticity of the Cp ring decreases linearly with the number
of substituents, the tetrasubstituted derivatives being the least
aromatic in each series. The inclusion of four hydroxyl groups
decreases signicantly the aromaticity of Cp ring increasing
the Euclidean distance from 9.9 to 33.1. The cyclopentadiene is
less sensitive to substitution than the Cp or Cp+, being
2,3,4,5-tetrauorocyclopentadiene the least aromatic of all
derivatives analyzed.
(b) All substituents reduce strongly the antiaromaticity of
cyclopentadienyl cation (Cp+), especially the electron-accepting
groups. The degree of antiaromaticity is determined by the
number and position of the substituents as well as their
electronic character. The great delocalization of positive
charge induced by the hydroxyl groups at positions 2- and 5stabilize Cp+ greatly. For all substituted cyclopentadienyl
cations the order of stability of regioisomers is controlled by
the antiaromaticity, so the most stable compound is the least
antiaromatic.
Overall, these results are important to learn about
structurearomaticity relationship or to anticipate putative
reaction intermediates as well as, from a practical perspective,
for devising new structures based on the cyclopentadienyl
cation with lowered instability and new ligands derived from
cyclopentadienyl anion with improved stability, reactivity and
catalytic activity.

Conclusions
In this paper, the usefulness of articial neural networks in the
evaluation of aromaticity/antiaromaticity of a broad set of
organic compounds is demonstrated, completing our previous
results.33,36 It has been proven that the Euclidean distance
between neurons is a reliable method to quantify both aromaticity and antiaromaticity of cyclopentadienyl substituted
compounds and, moreover, it overcomes the particular
drawbacks of the ASE, L, NICS and HOMA indices to
describe the changes in the aromaticity of cyclopentadiene
ring due to the substituent eects. This method is eective
since it comprehend the most used aromaticity descriptors
being able to apprehend the non-linear relationships between
them as well as the multidimensional character of the
aromaticity, what clearly constitutes an advantage over a
single aromaticity descriptors or any linear combination of
the descriptors, which have been reported to be unsuccessful.
Our results show that the Euclidean distance is useful for
establishing structure-property relationships, a general goal of
organic chemistry. The use of a single aromaticity descriptor
should be avoid because they has been proven to fail in
quantifying the degree of p-electronic delocalization of several
substituted cyclopentadienyl compounds.
The systematic study of the inuence of the substituent on
the aromaticity of a variety of anionic, neutral and cationic
derivatives of cyclopentadiene using self-organizing maps has
led to the following conclusions:
(a) The aromaticity of the cyclopentadiene (Cp) and cyclopentadienyl anion (Cp) ring decreases upon substitution
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Acknowledgements
This work was taken in part from the PhD thesis of M. A. and
it was nancially supported by the Spanish Ministry of
Education and Science (CTQ2007-64891/BQU). We would
like to thank Dr A. Chana for helpful discussions on neural
networks. We thank Dr J. D. Guillen for helpful assistance on
statistical analyses. M. A. thanks MEC for a FPU fellowship.
We also thank the Centro de Supercomputacion de Galicia
(CESGA) for computational time at the SVGD supercomputer.

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