物 理 化 学 学 报

692 Acta Phys. -Chim. Sin. 2018, 34 (6), 692–698

 
[Article] doi: 10.3866/PKU.WHXB201801121 www.whxb.pku.edu.cn

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning

Analysis

OROZCO-VALENCIA Ulises 1, GÁZQUEZ José L. 2, VELA Alberto 1,*

1 Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, Colonia San
Pedro Zacatenco, Ciudad de México, 07360, México.
2 Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México, 09340,

México.

Abstract: A global and local charge transfer partitioning model, based on

the cornerstone theory developed by Robert G. Parr and Robert G. Pearson,
which introduces two charge transfer channels (one for accepting electrons
(electrophilic) and another for donating (nucleophilic)), is applied to the
reaction of a set of indoles with 4,6-dinitrobenzofuroxan. The global analysis
indicates that the prevalent electron transfer mechanism in the reaction is a
nucleophilic one on the indoles, i.e., the indoles under consideration transfer
electrons to 4,6-dinitrobenzofuroxan. Evaluating the reactivity descriptors
with exchange-correlation functionals including exact exchange (global hybrids) yields slightly better correlations than
those obtained with generalized gradient-approximated functionals; however, the trends are preserved. Comparing the
trend obtained with the number of electrons donated by the indoles, and predicted by the partitioning model, with that
observed experimentally based on the measured rate constants, we propose that the number of electrons transferred
through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards
4,6-dinitrobenzofuroxan. This approach to obtain reactivity scales has the advantage of depending on the intrinsic
properties of the two reacting species; therefore, it opens the possibility that the same group of molecules may show
different reactivity trends depending on the species with which they are reacting. The local model allows systematic
incorporation of the reactive atoms based on the their decreasing condensed Fukui functions, and the correlations
obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic
charge improve, reaching an optimal correlation, which in the present case indicates keeping three atoms from the indoles
and two from 4,6-dinitrobenzofuroxan. The atoms selected by this procedure provide valuable information about the local
reactivity of the indoles. We further show that this information about the most reactive atoms on each reactant, combined
with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants, allows one to propose
non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions.

Key Words: Chemical reactivity; Conceptual DFT; Charge transfer; Nucleophilicity; Indoles, Transition state
prediction

1 Introduction energy of a chemical system is a smooth and differentiable

Chemical reactivity within density functional theory
(CRDFT) is a very active field that studies chemical
transformations 1–8. Aiming to justify the Hard-Soft
Acids-Bases principle (HSAB) 9, Parr and Pearson developed a
simple approach to study chemical reactivity assuming that the
function of the number of electrons that can be represented as a
quadratic function of this variable, we call this procedure the
Parr and Pearson model (PP) 10. This model is supported by the
Taylor expansion of the energy as a function of the number of
electrons keeping constant the external potential, leading to the

 
Received: November 24, 2017; Revised: December 29, 2017; Accepted: January 5, 2018; Published online: January 12, 2018.
*
Corresponding author. Email: avela@cinvestav.mx.
UOV was supported in part by Conacyt through a doctoral fellowship. JLG thanks Conacyt for grant 237045, and AV thanks Conacyt for grant Fronteras 867.
© Editorial office of Acta Physico-Chimica Sinica
No. 6 doi: 10.3866/PKU.WHXB201801121
1 differences: I = E(N – 1) − E(N) and A = E(N) − E(N + 1). This
emblematic PP expression E  N   ( N )2 for the
2 partitioning scheme has been successfully used to quantify the
change in the energy as a function of the change in the number
of electrons, ∆N, where μ and η are the electronic chemical
potential and the global hardness. This simple model has
explained many aspects of chemical reactivity that are well
documented in the literature. The change in the energy involved
in an association reaction such as A + B → AB can be
approximated as EAB  EA  EB , where the change in the
energy of each reactant is evaluated according to the expression
mentioned above for the change of the energy in terms of the
corresponding change in the number of electrons. Minimizing
∆EAB with respect to the amount of charge transferred and
using the constraint that the number of electrons is conserved,
one obtains that
B  A
N A   N B (1)
B  A
Considering that the global hardnesses of both species are
positive, the direction of electron flow is determined by the
chemical potential difference. Thus, if μA > μB then ∆NA < 0,
meaning that A is the nucleophile (species donating electrons)
and B the electrophile (species accepting electrons) 1,10.
According to Pearson if the number of electrons transferred in
an association reaction is large, it is likely that it may have a
low activation barrier, and he used this amount of charge
transferred to rationalize the reactivity of several organic and
inorganic reactions, founding a good correlation between Eq.
(1) with kinetic and equilibrium constants 11,12. The applicability
of this ansatz stands on the fact that the molecular structure of
the transition state is complied by the two fragments having
geometries very similar to those of the free reactants or, in
other words, that this reaction has an early transition state
(ETS), in agreement with Hammond’s postulate 13. In fact, this
is the scenario where one expects that CRDFT will have better
predicting capabilities 14,15.
Recently we presented a partitioning scheme for the number
of electrons exchanged in an association chemical reaction
considering that both species accept and donate charge, aiming
to determine the charge-transfer mechanism, electrophilic or
nucleophilic, prevailing in the reaction 16,17. We showed that the
global change in the number of electrons of reactant (fragment)
A can be written as
N A  N Anuc  N Aele (2)
where
AA  I B
N Anuc  (3)
2(A  B )
is the nucleophilic channel, and
AB  I A
N Aele   (4)
2(A  B )
the electrophilic channel. In Eqs. (3) and (4), I and A are the
vertical ionization potential and electron affinity, respectively,
of the corresponding species, that are determined by the energy
693 
amount of charge transferred by σ donation and π-back-
donation in transition metal (TM) ligand interactions 17. The
global charge transfer partitioning just described was
complemented with a local version that through the atomic
condensed Fukui functions of the reactants allowed us to
establish which are the most relevant atoms of each reactant
participating in the reaction 16. Therefore, in Ref.16 and Ref. 17
it is shown that this global and local partitioning provides
scales, through the amount of charge transferred that can serve
as alternative reactivity scales.
The aim of the present work is to apply this global and local
charge transfer partitioning model to explain the experimental
kinetic constants for a set of indoles studied by Mayr 18, paying
special attention to the conclusions provided by the analysis of
the most reactive atoms in these reactions.
2 Local model: a summary
In this section we very briefly describe the procedure that
leads to the working equations of the local model including the
partitioning that distinguishes charge transfer channels as
electrophilic or nucleophilic, for each reactant and leads to
determine which are the key atoms involved in the reaction. For
mathematical details we refer the reader to Ref. 16. The
derivation starts considering the functional Taylor expansion of
E[ρ(r)], truncated to second order, and assuming that the
changes in the electron density ∆ρ(r) are only due to electron
transfer; then ∆ρ(r) = f(r)∆N, where f(r) is the Fukui function
(FF) 19,20. Introducing an atomic resolution for the FFs we
obtain the following expression for the energy change of a
reactant
1
E  k  k  k fk [N  (N ) ]
2
(5)
2
where fk is the Condensed Fukui Function (CFF) of the k-th
atom in the corresponding molecule 21–24.
A key consideration in our local model is that we will not
include all atoms of each reactant in the evaluation of the
change in its energy. Instead, we will include a atoms from
reactant A and b atoms from reactant B. Therefore, the change
in the energy due to the changes on each reactant is given by
 ab          
a b
   A f [ A N A  12 A ( N A ) ] 
a 2
(6)

b
f  [  B N B  B ( N B ) ]
1 2
 B 2
where we use the subindex ab in ∆ε to indicate that this energy
change takes into consideration a atoms of reactant A and b
from reactant B. It is worth noting that when a and b are equal
to the total number of atoms in the reactants, Eq. (6) reduces to
the global model, as it should. The selection of atoms follows
the criterion that large values of the FF correspond to more
reactive sites in a chemical species. Thus, the atoms are ranked
694 Acta Physico-Chimica Sinica Vol. 34 

depending on their CFF values and the first to be included are
those with larger values of their CFFs. Minimizing Eq. (6) with
respect to ∆NA, using the constraint that the total number of
electrons is conserved leads to the following expression for the
amount of charge transferred to reactant A when considering a
atoms of A and b atoms of reactant B:
(  B   B f  )(  A   A f )
b a
In this section we apply the global and local charge transfer
partitioning model described above to the reaction between a
set of indoles and 4,6-dinitrobenzofuroxan (DNBF). These
reactions have been thoroughly analyzed by Mayr and his
group 18. The set of indoles, considered as reactants A, and
DNBF, as reactant B (the common substrate) are shown in Fig.
1. To determine which is the prevailing electron transfer

N A,ab  channel in the reaction, we analyze first the global charge

( B   B f  ) ( A   A f )
b a
(7)
  N B,ab
By assuming that the association reactions is such that A is
the nucleophile and B the electrophile, one can use the
nucleophilic CFF for atom α in A, f −α, and the electrophilic CFF
for atom β in B, f +β. Following the same partitioning procedure
used in the global model leads one to the following working
equations to evaluate the nucleophilic charge transferred when
considering a atoms of A and b atoms B:
transfer. In Table 1 we present the global reactivity indexes for
the indoles considered here and for DNBF, in addition to the
global charge transferred and the electrophilic and nucleophilic
partition charges evaluated by Eqs. (1), (3) and (4). Also shown
are the experimental kinetic constants taken from the work of
Mayr 18.
To determine which is the dominant charge transfer channel
in the reaction, in Ref. 16 we postulated that the prevailing
charge transfer channel is that where the amount of electrons

1 ( AA   A f )  (I B   B f  )
a
 b
 transferred goes parallel with the direction where the reactions
nuc (8)
N A,ab  proceeds faster. Hence, from the data reported in Table 1 we
2 (B   B f  )  (A   A f )
b a
conclude that the nucleophilic channel is the dominant electron
Proceeding analogously one can show that for the transfer mechanism in the reaction since the trend obtained
electrophilic channel,
1 ( I A A f )  ( AB   B f  )
a  b

ele (9)
N A, 
2 (B   B f  )  (A A f )
ab b a

Eqs. (8) and (9) are the working expressions that we will use
below to illustrate how they can be used to determine which are
the most important atomic sites of the reactants participating in
the reaction.
Fig. 1 a) Indoles with ―X (―NH2, ―OH, ―MeO,
―Me, ―H, ―Cl, ―CO2H, ―CN) substituents; b) DNBF.
3 Computational details Small letters label atoms of both molecules. For those indoles with
Unless otherwise stated, all calculations reported in this work substituents such as ―NH2, ―CN, ―OH, ―MeO, ―Cl, ―CO2H, label a
were made with Gaussian 09 (G09) 25 using the PBE functional 26,27 indicates the heavy atom different from carbon in the substituent group, i.e.,
and the 6-311G(d,p) basis set, and in gas phase. A frequency N, O, and Cl. 
analysis was done on every molecule to confirm that the Table 1 Global reactivity indexes, vertical ionization potential (I),
stationary points located by the optimization procedure were
electron affinity (A), chemical potential (μ) and hardness (η); total
minima in the potential energy surface. The CFFs were
charge transfer (∆N), electrophilic (∆Nele) and nucleophilic
determined through the response-of-molecular-fragment
charge-transfer (∆Nnuc) channels obtained with the PBE
approach 24, with Yang and Mortier’s scheme 21 where f +k =
exchange-correlation functional and the experimental kinetic
qk(N) −qk(N + 1) is the electrophilic CFF and f −k = qk(N − 1) −
constants taken from Ref. 18.
qk(N) is the nucleophilic CFF, and qk is the charge of the k-atom
―X IA AA μA ηA ∆NA ∆Nele
A ∆Nnuc
A lnk
in the molecule having N, N  1 and N  1 electrons. The
―NH2 6.8 −1.5 −2.7 8.3 −0.218 0.141 −0.359 5.46
atomic charges were obtained with Hirshfeld’s Population
―OH 7.3 −1.4 −3.0 8.7 −0.195 0.153 −0.347 3.50
Analysis (HPA) 28. The Fukui functions were evaluated
―MeO 7.2 −1.4 −2.9 8.6 −0.200 0.150 −0.350 3.04
following their the definitions 1,19: f −(r) = ρN(r) − ρN−1(r) for the
―Me 7.4 −1.4 −3.0 8.8 −0.190 0.155 −0.345 2.37
nucleophilic function, and f+(r) = ρN+1(r) − ρN(r) for the
―H 7.5 −1.4 −3.1 8.9 −0.183 0.158 −0.342 0.83
electrophilic function, where ρk(r) is the electronic density of
―Cl 7.7 −1.0 −3.4 8.7 −0.167 0.166 −0.334 −1.61
molecule having k = N, N  1 and N  1 electrons, respectively.
―CO2H 7.8 −0.6 −3.6 8.4 −0.154 0.173 −0.327 −2.75
For the rendering of the FFs we used VMD, version 1.9.1 29.
―CN 8.1 −0.5 −3.8 8.5 −0.140 0.180 −0.320 −5.65
IB AB μB ηA
DNBF 9.3 2.6 −5.9 6.7

4 Reactions between indoles and All energies are in eV. The subindexes A and B refer to the
4,6-dinitrobenzofuroxan corresponding reactant. 
No. 6 doi: 10.3866/PKU.WHXB201801121 695 

with ‫∆׀‬NAnuc‫ ׀‬is in general agreement with that observed in the
experimental kinetic constants. Therefore we can conclude that
nucleophilicity of indoles toward DNBF is the main electronic
process in the initial stages of these reactions. Fig. 2 depicts the
good correlation obtained between the nucleophilic charge
transfer channel and the experimental kinetic constants. This
provides graphical support to the previous conclusion: the
charge transfer mechanism prevailing in the reaction between
substituted indoles and DNBF is a nucleophilic one on the
indoles, i.e., in all cases they are donating charge to DNBF
through the nucleophilic channel. We can also suggest that
∆NAnuc can be used or considered as a nucleophilic scale for
indoles when reacting with DNBF given that the ordering
provided by this global descriptor is in agreement with the
scale presented by Mayr and collaborators 18. To illustrate the
role played by exact exchange in the prediction of the charge
transferred by our model, in Table 2 we report the global
reactivity indexes obtained using M06-2X 30 and the
6-311G(d,p)  basis set, and in Fig. 3 we depict the correlation
between the nucleophilic charge transferred predicted by this
functional and the experimental kinetic constants. One can see
that the trends are the same, independently of the exchange-
correlation functional, but the inclusion of exact exchange does
improve the correlations. With GGA (PBE) we obtain a value
of R2 = 0.978 and with a global hybrid (M06-2X), R2 = 0.982.
The reason for the improvement comes from the fact that the
vertical ionization potentials and electron affinities are better
predicted with global hybrids.
We now use the local model to illustrate its utility to identify
the most reactive atoms on each reactant. In Table 3 we show
the nucleophilic CFFs for the indoles considered in this work
and the electrophilic CFFs of DNBF. The atoms of both
reactants are labeled as shown in Fig. 1. For reasons that are
clarified below, we decided to select the seven larger values of
each reactant.
With the values of the CFFs shown in Table 3 and the
ionization potentials and electron affinities reported in Table 1,
the local nucleophilic channel for each indole was evaluated
according to Eq. (8) taking different combinations of reactive
atoms between indoles (a-atoms, first subindex) and DNBF
(b-atoms, second subindex). For each a and b combination of
atoms in the indoles and DNBF, respectively, we evaluated the
corresponding correlation coefficient (R2) between N A,ab
nuc

Fig. 2 Correlation between the PBE nucleophilic channel and the

experimental kinetic constants.
Values are from Table 1. The linear fit equation and the R2 correlation coefficient are

displayed on top of the plot.

Table 2 Global reactivity indexes, vertical ionization potential (I),

Fig. 3 Correlation between the M06-2X nucleophilic channel and the
electron affinity (A), chemical potential (μ) and hardness (η);
experimental kinetic constants.
total charge transfer (∆N), electrophilic (∆Nele) and nucleophilic
Values are from Table 2. The linear fit equation and the R2 correlation coefficient are
charge-transfer (∆Nnuc) channels obtained with the M06-2X
displayed on top of the plot.
exchange-correlation functional and the experimental kinetic
constants taken from Ref. 18. Table 3 The CFFs values for the indoles and DNBF according to the
―X IA AA μA ηA ∆NA ∆NAele ∆NAnuc Lnk atomic positions defined in Fig. 1.
―NH2 7.3 −1.6 −2.8 8.9 −0.214 0.143 −0.357 5.46 ―X 1 2 3 4 5 6 7
―OH 7.8 −1.5 −3.1 9.3 −0.191 0.154 −0.346 3.50 ―NH2 a 0.129 c 0.094 e 0.078 g 0.076 i 0.067 b 0.066 f 0.059
―MeO 7.7 −1.5 −3.1 9.2 −0.197 0.151 −0.349 3.04 ―OH a 0.105 c 0.104 e 0.099 g 0.087 i 0.076 b 0.073 f 0.065

―Me 7.9 −1.6 −3.1 9.4 −0.190 0.155 −0.345 2.37 ―MeO a 0.094 c 0.094 e 0.086 g 0.082 b 0.069 i 0.068 f 0.059

―H 8.0 −1.6 −3.2 9.5 −0.185 0.158 −0.342 0.83 ―Me e 0.119 c 0.098 i 0.088 f 0.086 g 0.084 j 0.066 b 0.059

―Cl 8.2 −1.1 −3.6 9.3 −0.165 0.167 −0.333 −1.61 ―H e 0.123 f 0.099 c 0.097 i 0.091 j 0.085 g 0.079 b 0.066

―CO2H 8.3 −0.8 −3.7 9.1 −0.158 0.171 −0.329 −2.75 ―Cl a 0.161 e 0.112 c 0.094 g 0.085 i 0.080 f 0.074 b 0.056

―CN 8.6 −0.7 −4.0 9.2 −0.142 0.179 −0.321 −5.65 ―CO2 e 0.120 f 0.098 i 0.087 c 0.083 j 0.079 g 0.075 a 0.050

IB AB μB ηB ―CN e 0.117 a 0.114 c 0.088 f 0.083 i 0.082 g 0.081 j 0.062

DNBF 9.8 2.7 −6.3 7.1 DNBF d 0.103 c 0.085 a 0.079 g 0.078 f 0.075 b 0.073 e 0.071

All energies are in eV. The subindexes A and B refer to the corresponding reactant.  From left to right, the columns are ordered by decreasing values of the CFFs.
696 Acta Physico-Chimica Sinica Vol. 34 

and the experimental kinetic constants. These correlations
coefficients are reported in Table 4.
Table 4 shows two clear tendencies. First, when increasing
the number of reactive atoms in the indoles (index a),
independently of the number of reactive atoms considered in
DNBF, the correlation coefficients increase monotonically, i.e.,
they have better correlations. Secondly, and in contrast with the
previous observation, the situation is completely opposite with
respect to DNBF where, in all cases, the correlations decrease
monotonically as more reactive atoms in DNBF are considered.
The global picture indicates that for these reactions the best
correlation would correspond to that obtained with the global
partitioning or, in other words, to include all atoms in the
evaluation of the N A,ab . In our previous applications of
nuc
the model we found that there was an optimum number of
atoms on each reactant providing the maximum correlation and,
consequently, going beyond this number of atoms worsened the
correlations. Thus, in the present case, considering that the
global correlation is very good and that the main intention with
the local partitioning is to identify the most reactive atoms in
the reactants, we decided to limit the number of atoms in the
indoles to seven. In fact, to provide a more concrete selection
of reactive sites one could limit the number of relevant atom to
4 considering that Table 4 shows that the improvement in the
correlations is marginal when the number of atoms in the
indoles goes beyond a = 3. Then, using the combination ab =
32, i.e., taking the first three atoms in the indoles and the 2
atoms in DNBF that have the larger values of the CFFs, and
from the data reported in Table 3, we find that the atoms
playing the most important roles in the reaction are: in the
indoles atoms a, c, e, f, and i; in DNBF, atoms c and d.
Considering the most frequent appearance of the atoms in the
eight indoles we can say that atoms c and e are the most likely
atoms to participate in the reaction. It should be noted that for
indoles with electron donating substituents the atom different
from carbon in the group is, according to their CFFs values, the
most likely atom to suffer the attack.
We now use the information obtained above regarding the
most reactive atoms together with spatial distribution of the FFs
to propose a plausible starting geometry orientation between
indoles and DNBF that could drive the system to the transition
state. In Fig. 4 we present isosurface plots of the electrophilic
and nucleophilic FFs of one indole (X  ―H) and DNBF.
According to Fig. 4a the initial intermolecular binding between
indoles and DNBF happens on the molecular plane since this
orientation seems to maximize the overlap between the FFs;
note that the nucleophilic FF of the indole covers the zone of
C(e) atom and, moreover, the electrophilic FF of DNBF also
covers the C(c) and C(d) atoms. Second, in Fig. 4b we show the
isovalue plots of the electrophilic FF of the indole and the
nucleophilic one of DNBF. These plots can provide further
support to propose a molecular orientation in the binding
between the indole and DNBF. In this case, the isosurface plots
suggest that the overlap between the oxygen atom (position d)
in DNBF and the carbon atom of the indole in position f are the
most likely interacting sites. It is important to comment that
this oxygen atom in DNBF has also a large negative charge in
addition to a large nucleophilic CFF value, and that the carbon
atom of indole in position f also has a low negative charge and
a large electrophilic CFF value. This interaction by alienation
of nucleophilic/electrophilic zones of DNBF and indole is
feasible due to the proximity between C(e) and C(f) atoms in
the indole. Moreover, note that the intermolecular binding
suggested by our analysis and the alienation of nucleophilic/
electrophilic zones between indole and DNBF produces a
six-member ring that can stabilize this structure and makes it a
good candidate to start searching for the TS of the reaction.
Therefore, these isosurface plots of the FFs of indole and
DNBF together with the knowledge about the most reactive
atoms we can propose that the attack of the indole on DNBF
may occur as shown in Fig. 5. Similar findings were obtained
for the other indoles.
It is important to note that this analysis about the initial
stages of the reaction mechanism between indoles and DNBF is

Table 4 Correlations coefficients (R2) between the local nucleophilic

channel of indoles and the experimental kinetic constants, for different
combinations of reactive atoms in the indole (a) and in DNBF (b).
a
b
1 2 3 4 5 6 7
1 0.60 0.88 0.94 0.96 0.97 0.97 0.97

2 0.49 0.81 0.90 0.94 0.96 0.97 0.97

Fig. 4 Isosurface plots of the Fukui Function (nucleophilic in red and
3 0.45 0.76 0.86 0.91 0.94 0.96 0.96
electrophilic in blue), using an isovalue of 0.007, for the indole with
4 0.42 0.73 0.83 0.89 0.92 0.95 0.95
X  ―H and DNBF.
5 0.40 0.71 0.81 0.87 0.91 0.93 0.94
a) Orientation suggested by the nucleophilic FF of the indole and the electrophilic FF of
6 0.39 0.70 0.79 0.85 0.89 0.92 0.93
DNBF, and b) orientation suggested by the electrophilic FF of the indole and the
7 0.38 0.68 0.78 0.84 0.88 0.91 0.92
nucleophilic FF of DNBF. The most reactive atoms are also labeled in both plots.
No. 6 doi: 10.3866/PKU.WHXB201801121
Fig. 5 Schematic representation of the interaction between
indoles and DNBF.
The red solid line indicates the binding sites and the red dashed line indicates the
alienation of the electrophilic carbon atom in the indoles and the nucleophilic
oxygen atom in DNBF.
in agreement with the experimental evidence about the
intermolecular binding site between reactants 31. Moreover, our
conclusion that the nucleophilicity of indoles controls its
reactivity towards DNBF is also in agreement with the
experimental results of Mayr and other theoretical works using
CRDFT 18,32.
5 Summary and conclusions
In this work we applied a global and local partitioning model
of charge transfer to the nucleophilicity of indoles reacting with
4,6-dinitrobenzofuroxan. The global model leads us to
conclude that the reaction is controlled by a nucleophilic attack
on the indoles, in agreement with the experimental conclusion.
The nucleophilic charge transferred is in excellent agreement
with the nucleophilic ordering proposed by Mayr and
collaborators suggesting that this global reactivity index can be
used as nucleophilic scale for the reactivity of indoles. The
local analysis of the nucleophilic channel indicates that the
atoms playing the most relevant roles in the reactions are C(c)
and C(e) of indoles and the C(c) of 4,6-dinitrobenzofuroxan.
Using the information provided by the local analysis and the
spatial distribution of the electrophilic and nucleophilic Fukui
functions of the indoles and 4,6-dinitrobenzofuroxan, we show
that one can suggest molecular structures that can describe the
first stages of the interactions between these reactants that can
be used as starting geometries for the transition state search of
these reactions. The analysis suggests the existence of an
alienation of nucleophilic/electrophilic zones between indole
and DNBF that produces a six-member ring.
Acknowledgment: We thank the Laboratorio Nacional de
Cómputo de Alto Desempeño (LANCAD) for the use of their
facilities.
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