Electrochimica Acta 81 (2012) 197–204

Contents lists available at SciVerse ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical and chemical formation of a low-barrier proton transfer

complex between the quinone dianion and hydroquinone
Pablo D. Astudillo a , Drochss P. Valencia a , Miguel A. González-Fuentes a , Blanca R. Díaz-Sánchez a ,
Carlos Frontana b , Felipe J. González a,∗
a
Departamento de Química del Centro de Investigación y de Estudios Avanzados del I.P.N., Apartado Postal 14-740, 07360, México, D.F., Mexico
b
Centro de Investigación y Desarrollo Tecnológico en Electroquímica, Parque Tecnológico Querétaro, Sanfandila, 76703, Pedro Escobedo, Querétaro, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: The electrochemistry of the 1,4-benzoquinone and hydroquinone in acetonitrile and dimethylsulfox-
Received 19 April 2012 ide was reviewed to explain the nature of a broad reversible signal that appears during the reduction
Received in revised form 21 July 2012 of quinones with small amounts of proton donors and that cannot be explained in the framework of
Accepted 21 July 2012
the classical mechanisms of quinone reduction. Cyclic voltammetry and NMR experiments as well as
Available online 27 July 2012
electronic structure calculations were performed to show that under specific conditions, the anion QH−
disproportionates into a face-to-face dianionic quinhydrone associated by strong intermolecular hydro-
Keywords:
gen bonds. This complex explains the mentioned broad signal and the results presented show that it can
Quinone
Quinhydrone
be formed during the reduction of benzoquinone in the presence of stoichiometric amounts of weak pro-
Proton transfer ton donors such as acetic acid and hydroquinone, or by half-deprotonation of hydroquinone. An analysis
Hydrogen bonding of the energetic barriers of the hydroxyl protons involved in the complex is also presented in this work.
Charge transfer complex © 2012 Elsevier Ltd. All rights reserved.

1. Introduction of electrochemical studies with the aim to understand the differ-

The quinone moiety is a redox active cofactor whose bidirec-
tional conversion into hydroquinone plays a key role in biological
electron and proton transport processes, such as those occurring
at mitochondria, chloroplasts and bacterial cell membranes [1–4].
Important examples of the biological activity of these lipid soluble
electron and proton carriers are found in literature, for instance,
in the redox cycle of vitamin K [5–7], in the respiratory chains
of aerobic organisms where mitochondrial NADH:ubiquinone oxi-
doreductase (complex I), cytochrome bc1 oxidoreductase (complex
II) and succinate-quinone reductase (complex III) are important
components [8–11] and also in the process of photosynthesis in
chloroplasts where plastoquinone or phylloquinone are the redox
cofactors [12–14]. The electron transfer properties of quinones
have also important implications in cellular defense since they
show antibacterial [15,16], antifungal [17,18] and antiparasitic
properties [19,20]. It is also remarkable that the quinone structure
and the functional groups involved in the quinonoid structure are
both essential to develop specific biochemical functions such as
cytotoxicity and anticancer activity [21,22].
The importance of the quinone-to-hydroquinone bidirectional
conversion in biological systems has motivated a great number
∗ Corresponding author. Fax: +52 55 57473389.
E-mail address: fgonzale@cinvestav.mx (F.J. González).
ent molecular factors determining the stability or reactivity of the
reduced species. The studies on the electrochemical behaviour of
quinones have been performed in buffered [23] and unbuffered [24]
aqueous media as well as in polar organic solvents [25,26].
It is known that the basicity and nucleophilic power of the
reduced quinonoid species are intrinsically related with the final
reactivity of these intermediates. These chemical properties can
be modified by the presence of electron-releasing or electron-
withdrawing substituents on the quinone structure [27–29] or
through the establishment of intramolecular hydrogen bonds,
such as in the case of ␤-hydroxynaphthoquinones [30–34]. For
quinones not substituted with acidic functional groups (Q), the
electrochemical reduction in aprotic solvents is carried out fol-
lowing two quasireversible consecutive one-electron transfer steps
[35]. Under these conditions, the electrochemically generated
semiquinone radical anion (Q•− ) and the dianion (Q2− ) are sta-
ble and both can be directly detected on the reverse scan in
cyclic voltammetry experiments [25]. The structural properties
of these fundamental intermediates have been established from
electrochemical methods coupled with UV–vis [36,37], FTIR [38],
ESR [39,40] and NMR [40] spectroscopies. As an external fac-
tor contributing to the stabilization of these intermediates, the
association with metallic cations [41–43] and weak hydrogen
bonding donors has been demonstrated for many quinonoid
systems [36,44–47]. Additionally, stabilization effects by ␲–␲
type charge transfer interactions have also been reported in

0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.07.078
198 P.D. Astudillo et al. / Electrochimica Acta 81 (2012) 197–204

the case of the dianion species and aromatic hydrocarbons

[48].
When the reduction process of quinones is carried out in apro-
tic solvents in presence of an excess of moderately strong proton
donor (DH) such as carboxylic acids, the quinone is directly trans-
formed into hydroquinone QH2 , which is strongly associated with
the conjugated base of the proton donor D− [49]. The generally
accepted mechanism for a wide variety of quinones and proton
donors involves two electron and two proton transfer reactions,
which occur in the framework of the classical square scheme (ECEC)
competing with first or second order disproportionation mecha-
nisms (DISP1 or DISP2) [25,50].
The transition from the one electron transfer process in apro-
tic medium towards the two-electron and two-proton transfer
mechanism in acidic medium has revealed new insights about the
overall mechanism of the quinone-to-hydroquinone bidirectional
conversion. For example, when the concentration of the proton
donor is close to the quinone concentration, a broad peak between
those corresponding to the formation of semiquinone and quinone
dianion has been observed [51]. The species involved in the clas-
sical electron and proton transfer scheme are not able to explain
the appearance of this broad peak. However, the intervention of Fig. 1. Cyclic voltammetry of 1,4-benzoquinone 2 mM in the presence of several
concentrations of acetic acid, in acetonitrile + n-Bu4 NPF6 0.2 M, on a glassy carbon
an anionic complex, analogue to the well known charge trans-
electrode ( = 3 mm) at 0.1 V s−1 .
fer system quinhydrone [52], was consistent with this unexpected
peak. Thus, in the present work, the nature of this anionic type-
quinhydrone complex, which is a good example of a low-barrier electrode; this electrode was polished with 1 ␮m alumina powder
proton transfer complex, was studied in acetonitrile and dimethyl- (Buehler) and ultrasonically rinsed with anhydrous ethanol before
sulfoxide. Three ways to prepare and analyse the proposed complex each run. The counter electrode was a platinum mesh and the ref-
were considered: (1) in situ formation during the reduction of 1,4- erence electrode an aqueous saturated calomel electrode (SCE). A
benzoquinone in the presence of sub-stoichiometric amounts of salt bridge, containing a solution of 0.1 M n-Bu4 NPF6 in either ace-
acetic acid, (2) formation during the association of hydroquinone tonitrile or DMSO, was used to connect the cell with the reference
with the quinone dianion generated by electrochemical reduction electrode.
1 H and 13 C NMR spectra were recorded on a Jeol GSX-270 spec-
of benzoquinone and, (3) by half-deprotonation of hydroquinone.
These studies were carried out by cyclic voltammetry, 1 H NMR trometer in deoxygenated deuterated acetonitrile.
spectroscopy and electronic structure calculations.
2.3. Calculations
2. Experimental
Geometry optimization and frequency calculations of the
dianion–hydroquinone and monoanionic–monoanionic complexes
2.1. Chemicals and procedures
were carried out with the program Gaussian 09 Revision B.01 [53],
using the approach of the Density Functional Theory. Four differ-
1,4-Benzoquinone 99%, hydroquinone 99%, acetic acid 99%,
ent functionals were employed: BHandHLYP [54], MPW1PW1 [55],
tetrabutylammonium hydroxide 1 M/methanol and tetraethy-
MPW1PBE [56] and the long range corrected PBE functional, LC-
lammonium hydroxide 1 M/water were Aldrich chemicals. 1,4-
PBE [57–60], with a 6-311++G(d,p) basis set. Frequency analysis
Benzoquinone was previously purified by sublimation under
for all the involved structures were performed after full geometry
reduced pressure. Acetonitrile and dimethylsulfoxide spectropho-
optimizations, revealing the absence of negative frequencies, thus
tometric grade (Merck Uvasol) were the solvents used for the
indicating that the structures are minimum energy conformers.
electrochemical and spectroscopic experiments and they were
used as received. Tetrabutylammonium hexafluorophosphate 98%
(Aldrich), recrystallized from absolute ethanol and vacuum-dried 3. Results and discussion
overnight in a Schlenck tube at ∼80 ◦ C, was used as the sup-
porting electrolyte. The hydroquinone deprotonation was carried 3.1. Electrochemical reduction of 1,4-benzoquinone in presence
out in inert atmosphere by using tetrabutylammonium hydroxide. of acetic acid
The chemical and electrochemical experiments were performed at
room temperature (∼25 ◦ C). All the working solutions were deoxy- The electrochemical behaviour of 1,4-benzoquinone (Q) in ace-
genated with dry argon bubbling directly to the bulk solution before tonitrile, in absence and in presence of acetic acid (HAc), is shown
every voltammetric scan, keeping the inert atmosphere in the cell in Fig. 1. In aprotic media (Fig. 1a), two typical consecutive one-
during each experiment. electron quasi-reversible peaks, affording the radical anion Q•−
and dianion Q2− , were observed. Peaks Ic–Ia (E1o = −0.498 V vs SCE)
correspond to the redox couple Q/Q•− (Eq. (1)) while peaks IIc–IIa
2.2. Instrumentation, cell and electrodes (E2o = −1.239 V vs SCE) correspond to the couple Q•− /Q2− (Eq. (2))
[25,35].
A DEA-332 potentiostat (Radiometer, Copenhagen) was used
for all the electrochemical experiments applying positive feedback Eo •−
1
Q + e− Q (1)
resistance compensation. Voltammetric experiments were carried
out on a conventional three-electrode cell. A 3 mm diameter glassy •−
Eo
− 2
carbon disk (Sigradur G, from HTW Germany), was used as working Q + e Q2− (2)
 P.D. Astudillo et al. / Electrochimica Acta 81 (2012) 197–204
Alternatively, in the presence of an excess of acetic acid (Fig. 1d),
the second reversible reduction wave IIc–IIa disappears while the
first reversible wave Ic–Ia becomes a less negative chemically irre-
versible wave IIIc (Ep = −0.245 V vs SCE at 0.1 V s−1 ) that involves
the well known two-electron and two-proton transfer mechanism
[25], which occurs in the framework of the classical competition
between the ECEC (Eqs. (1), (3)–(5)) and disproportionation (Eqs.
(1), (3), (4 ), and (5)) mechanisms [61]. The disappearance of wave
IIc–IIa as well as the transition of wave Ic into wave IIIc is in agree-
ment with the fact that QH• is more easily reduced than Q (E4o > E1o ).
As a result of this condition, the current peak of wave IIIc corre-
sponds approximately to a two-fold increase compared with the
peak current of wave Ic.
•−
Q + e−  Q
•− •
Q + HAc  QH + Ac−
•
QH + e−  QH−
and/or
• •−
QH + Q  QH− + Q
QH− + HAc  QH2 + Ac−
Q + 2e− + 2HAc = QH2 + 2Ac−
Due to the fact that acetate ion (Ac− ) and hydroquinone (QH2 )
are simultaneously produced in the overall reaction mechanism
of Eq. (6) (Eqs. (1) + (3) + (4) + (5) or (1) + (3) + (4 ) + (5)), a hydrogen
bonding association complex, QH2 (Ac− )2 , is formed. This complex
is oxidized at the level of peak IIIa (Fig. 1), whose oxidation peak
potential can range from −0.078 to 0.241 V vs SCE depending on
the acetic acid concentration. The magnitude of this potential is
lower than that of free hydroquinone under the same experimental
conditions (Ep = 1.027 V vs SCE at 0.1 V s−1 ) [49].
During the transition from one-electron towards two-electron
transfer mechanisms, the most interesting feature of the voltam-
metric behaviour was obtained at stoichiometric concentrations of
HAc ([HAc]/[Q] ≤ 1) (Fig. 1b and c). Under these conditions, the last
protonation step of the mechanism (Eq. (5)) cannot be favoured
and consequently the anion QH− should be the only expected
species, such as depicted by the overall Eq. (7) (Eqs. (1) + (3) + (4)
or (1) + (3) + (4 )).
In the literature, an oxidation peak like IIIa has been sometimes
assigned to the species QH− [26]. However, the problem with this
proposal arises from the fact that this oxidation peak corresponds
rather to the voltammetric response of the association complex
between QH2 and the conjugated base of acetic acid [49]. Therefore,
an alternative process is occurring with QH− at stoichiometric con-
centrations of HAc and this must be related to the presence of the
unexpected broad peaks IVc–IVa (Epc = −0.831 and Epa = −0.724 V
vs SCE) in Fig. 1, which appears between the redox signals of Q/Q•−
(Ic–Ia) and Q•− /Q2− (IIc–IIa).
At this point, the main feature of the results carried out at
sub-stoichiometric and stoichiometric concentrations of HAc, con-
sists in the fact that the occurrence of peaks IVc–IVa cannot be
explained by any of the species involved in the two-electron and
two-proton transfer mechanisms (Eqs. (3)–(6) and/or (3), (4), (5),
(6)). Nevertheless, these results suggest that the species QH− must
be related in some way to that occurring in peak IVc–IVa. There-
fore, to obtain information about the electrochemical behaviour of
QH− , but in a more simplified experimental system, the product of
half-deprotonation of QH2 with tetrabutylammonium hydroxide
was analysed.
199
(3)
(4)
(4 )
(5)
(6) Fig. 2. Cyclic voltammetry of hydroquinone 2 mM in the presence of tetrabutylam-
monium hydroxide, in acetonitrile + 0.2 M n-Bu4 NPF6 , on glassy carbon electrode
(3 mm ␾) at 0.1 Vs−1 . The concentration of n-Bu4 NOH was (A) 0 mM, (B) 2 mM and
(C) 4 mM.
3.2. Chemical formation of a quinone dianion–hydroquinone
complex
In order to understand the nature of peaks IVc–IVa, the electro-
chemical behaviour of pure hydroquinone QH2 in acetonitrile was
recorded (Fig. 2A). The typical two-electron oxidation peak IIIa [49]
was observed, which is chemically irreversible and is located at a
peak potential value of Ep = 1.027 V vs SCE at 0.1 V s−1 . Signal IIIc is
related to reduction of protonated 1,4-benzoquinone, which is the
product formed at the level of peak IIIa [49].
Fig. 2B shows the voltammogram corresponding to the product
of half-deprotonation of QH2 , which in principle, should correspond
to the anion QH− . Starting from the highly negative open circuit
potential value (ocp = −0.938 V vs SCE) and scanning towards the
positive direction, the anodic segment of the broad peak IVa was
found to be coincident with peak IVa of Fig. 1C, obtained by reduc-
tion of Q in presence of stoichiometric amounts of HAc. As shown in
Fig. 2B, the oxidation (at the level of peak IVa) of the product of half-
deprotonation of hydroquinone (in principle a species derived from
QH− ) gives rise to semiquinone Q•− (peak Ia) and hydroquinone
QH2 (peak IIIa). This result and the fact that the peak potential of
IVa (Ep = −0.724 V vs SCE at 0.1 V s−1 ) is quite negative and it occurs
at a potential similar to that for the oxidation of quinone dianion
Q2− (peak IIa in Fig. 2C) (Epa = −0.881 V vs SCE at 0.1 V s−1 ), allows
to propose that QH− is not stable under the experimental condi-
tions and therefore it disproportionates to afford a sort of dianionic
face-to-face dimeric complex, as proposed in Eq. (7).
 
2QH− → Q2− , QH2 (7)
The proposed complex can be viewed as a dianionic quinhy-
drone, which must involve two hydrogen bonding interactions, but
stronger than in the case of neutral quinhydrone. We have assumed
[Q2− · · ·QH2 ] as notation for this complex; however, the structure
should be rather that corresponding to a low barrier proton transfer
200 P.D. Astudillo et al. / Electrochimica Acta 81 (2012) 197–204
_ _
O H O O H O
_O H O _O H O
_ _ _ _
[Q 2 ... QH ]
2
[QH ... QH ]
Scheme 1. Resonant structures of the quinhydrone-type dianionic complex.
complex, which can be represented by several resonant structures,
as shown in Scheme 1.
These strong interactions are commonly found when a proton is
shared between two equivalent electronegative atoms, where one
of them is negatively charged [62]. Due to the electrostatic nature
of the interaction, it can also be proposed that the occurrence of
the disproportionation process of QH− (Eq. (7)) is possible because
of the complex is stabilized through two strong hydrogen bond-
ing interactions. Although more details about the structure of this
complex will be discussed later from the point of view of electronic
structure calculations, it can be mentioned that an analogue exam-
ple of face-to-face dimeric complex, but positively charged, was
recently reported by Smith and coworkers for the case of proto-
nated phenylendiamines [63].
The proposal of the quinhydrone-type dianionic complex is then
useful to explain the behaviour of the half-neutralization product
of QH2 . As shown in the voltammogram of Fig. 2B, the complex
is oxidized at the level of peak IVa, to afford a transient associated
radical anion [Q•− · · ·QH2 ], which is dissociated into the free species
Q•− and QH2 (Eqs. (8) and (9)). In this way, the radical anion Q•− is
oxidized at peak Ia while QH2 is oxidized at peak IIIa. It is remark-
able that the current intensity of IIIa in Fig. 2B is approximately the
half of that observed in Fig. 2A, which is in agreement with the fact
that the complex was prepared from two equivalents of QH2 while
only one equivalent of this one is released from the oxidation of
complex at peak IVa.
 2−
 −
 •−  measurements
Q , QH2 − e  Q , QH2
 •−  •−
Q , QH2  Q + QH2
Several studies of association of semiquinone and quinone dian-
ion with weak proton donors have led to conclude that hydrogen
bonding interactions with the dianion are stronger than in the case
of semiquinone [44–46], which supports the proposal that the rad-
ical anion complex [Q•− · · ·QH2 ] is dissociated according to Eq. (9).
As shown in the voltammogram of Fig. 2B, where the potential scan
is inverted at 0 V vs SCE, the chemical reversibility of waves Ia–Ic
indicates that dissociation of [Q•− · · ·QH2 ] is indeed highly favoured.
Considering that the position of the peaks of quinones can be shifted
towards less negative values by effect of hydrogen bonding inter-
actions, the invariance in the position of waves Ia–Ic in Fig. 2B with
respect to those of Fig. 2C, in which the free species Q•− and Q2−
are involved, suggests that the association equilibrium constant
between Q•− and QH2 must be in fact very small.
In order to obtain chemical information about the species giv-
ing rise to the broad peak IVa of Figs. 1 and 2, the product of
half-deprotonation of hydroquinone was studied by 1 H NMR spec-
troscopy in deuterated acetonitrile (Fig. 3).
Considering that low contents of water does not modify
the electrochemical behaviour in a relevant way, as observed
in Figs. 1 and 2, the hydroquinone was directly deprotonated
with tetraethylammonium hydroxide before the 1 H NMR spectra
recording. Due to the fact that the voltammetric behaviour of the
product of half-neutralization of QH2 with base is identical for solu-
tions 2 mM and 8 mM, the 1 H NMR experiments were performed
at this last concentration. Fig. 3A shows the spectrum of QH2 in
_ _
O H O O H O 2
_O H O O H O
_ _
[QH ... QH ] [Q ... H,H ... Q] 2
pure deuterated acetonitrile, which presents the signals of water
and acetonitrile at high field and the signals for hydroquinone at
6.63 ppm (C H) and 6.46 ppm (O H). The first signal corresponds to
the aromatic protons and the second one to both hydroxyl protons.
In the case of the product of half-neutralization of QH2 with the
base (Fig. 3B), the signals for water and deuterated acetonitrile were
also observed, as well as the signals related to the ethyl group of the
tetraethylammonium cation, that is, the triplet and quartet corre-
sponding respectively to the methyl (CH3 1.19 ppm) and methylene
groups (CH2 3.13 ppm). In the same spectra, the signal appearing at
6.58 ppm is assigned to the aromatic protons in the complex due to
the fact that it is very close to that found for pure QH2 (6.63 ppm).
The presence of this simple signal at 6.58 ppm and the absence of
any signal corresponding to the O H protons, indicates that the
product of half deprotonation should be symmetrical. Additionally,
the fact that no signal was found for these protons even at very low
field (up to 25 ppm), suggests also that these protons participate
in an equilibrium involving a strong hydrogen bonding interaction
[62]. In agreement with the electrochemical results, the 1 H NMR
study suggests also that the product of half-deprotonation of hydro-
quinone is the dianionic quinhydrone linked by strong hydrogen
bonds in which each hydrogen atom is in fast exchange between
two oxygen atoms, as depicted in Scheme 1.
3.3. The dimeric nature of complex by diffusion coefficient
(8)
The dimeric nature of the product of half-deprotonation of
(9)
hydroquinone can be evidenced considering that the diffusion coef-
ficient of complex must be smaller than that of the hypothetical
species QH− . Thus, an estimation of the molecular weight of species
[Q2− · · ·QH2 ] giving rise to peak IVa has been carried out through dif-
fusion coefficient measurements. Such estimation in acetonitrile is
possible by using a previously reported linear correlation between
the diffusion coefficient and the molecular weight for a family of
quinones, nitroaromatic compounds, aromatic compounds and fer-
rocene derivatives (Fig. 4) [64]. The use of such correlation in our
case is reliable because the molecular density of the target complex
must be comparable to the average molecular density found for the
family of compounds used to construct the mentioned correlation.
Single potential step chronoamperometry has been used to
determine the diffusion coefficient of complex [Q2− · · ·QH2 ], tak-
ing as reference the experiment depicted in Fig. 2A. Owing to the
fact that peak IVa is too close to peak Ia, we decided to apply a
potential step at −0.265 V vs SCE, where pure diffusion conditions
are established. According to the voltammogram of Fig. 2B, it has
been considered that one electron is consumed for the oxidation
of [Q2− · · ·QH2 ] while an additional electron is consumed for the
oxidation of semiquinone Q•− . Therefore, the calculation of the
diffusion coefficient from the Cottrell behaviour was performed
assuming that the electron number is 2. Upon these considera-
tions, the diffusion coefficient of [Q2− · · ·QH2 ] was determined to
be (1.97 ± 0.07) × 10−5 cm2 s−1 .
Fig. 4 shows the linear correlation between the diffu-
sion coefficient and the molecular weight that we have
 P.D. Astudillo et al. / Electrochimica Acta 81 (2012) 197–204
Fig. 3. 1 H NMR spectrum in deuterated acetonitrile. (A) QH2 8 mM in pure deuterated acetonitrile, (B) Product of half-neutralization of QH2 8 mM with tetraethylammonium
hydroxide.
previously reported [64], whose fitting equation is given by
D[cm2 s−1 ] = 3.52 × 10−5 − 6.59 × 10−8 (Mw). The use of this equa-
tion and the experimental diffusion coefficient have permitted to
extrapolate a value of the molecular weight of complex [Q2− , QH2 ],
which was about MW = 235.5. This value is very close to the the-
oretical molecular weight of the proposed complex (MW = 218.2).
This comparison represents additional evidence supporting the
proposal of a dianionic-type quinhydrone dimeric complex for
the product of half-deprotonation of hydroquinone, which was
Fig. 4. Plot of the diffusion coefficient of quinones, aromatic hydrocarbons, aro-
matic nitrocompounds and ferrocene derivatives, in acetonitrile +0.1 M n-Bu4 NPF6
at 25 ◦ C, against its respective molecular weight [64].
201
considered to be the result of disproportionation of the anion QH− ,
such as it was depicted by Eq. (7).
3.4. The role of solvent on the complex formation
The electrochemical oxidation of hydroquinone is sensitive to
the nature of solvents such as acetonitrile and dimethylsulfoxide,
whose hydrogen bonding acceptor properties influence the rate of
proton cleavage involved in the reaction mechanism [49]. In this
way, it is interesting to investigate the effect of DMSO on the forma-
tion and stability of the quinone dianion–hydroquinone complex.
Fig. 5 shows the voltammograms obtained in acetonitrile and
DMSO for the proposed complex, which is the half-deprotonation
product of hydroquinone. By comparing Fig. 5A and B, it is observed
that the general features of both voltammogramms are essentially
the same, suggesting that the complex is also formed in DMSO
and it follows an oxidation mechanism analogue to that found in
acetonitrile, giving rise to the formation of semiquinone Q•− and
hydroquinone QH2 (Eqs. (8) and (9)). However, some variations in
the position of peaks are observed. For example, the oxidation peak
IIIa is shifted towards less positive values in DMSO because this sol-
vent increases the deprotonation of the radical cation QH2 •+ formed
during the first electron transfer step of the oxidation mechanism
of QH2 [49]. Concerning peaks Ia–Ic, they are slightly less negative
in DMSO, an effect that has been attributed to stabilization of Q•−
by effect of the larger solvation capacity of DMSO with respect to
acetonitrile [65].
Concerning the broad peaks IVa and IVc, in DMSO, they were
more negative (Epa = −0.746, Epc = −0.994 V vs SCE) than in the
case of acetonitrile (Epa = −0.626, Epc = −0.870 V vs SCE). The shift
of the peak potential IVa towards more negative values can be
202 P.D. Astudillo et al. / Electrochimica Acta 81 (2012) 197–204
Fig. 5. Cyclic voltammetry of hydroquinone 2 mM in the presence of tetrabuty-
lammonium hydroxide 2 mM, in acetonitrile (A) and dimethylsulfoxide (B), +0.2 M
n-Bu4 NPF6 , on glassy carbon electrode (3 mm ␾) at 0.1 Vs−1 .
explained by considering that semiquinone Q•− and hydroquinone
QH2 are both stabilized, the former by solvation with DMSO,
and QH2 through interaction with this hydrogen bonding accep-
tor solvent. On the contrary, in the case of peak IVc, this signal
is the result of the reduction of semiquinone to Q2− coupled
with strong association equilibrium with QH2 . The peak poten-
tial IVc is more negative in DMSO than in the case of acetonitrile
because the hydrogen bonding interaction between QH2 and DMSO
is unfavourable for the quinone dianion–hydroquinone complex
formation. This result suggests the possibility to generate the
quinone dianion–hydroquinone complex during the reduction of
1,4-benzoquinone in the presence of hydroquinone. Since the broad
peaks IVa–IVc are more separated from the quinone–semiquinone
peaks in DMSO, this solvent was used for such experiments.
3.5. Complex formation during reduction of benzoquinone in
presence of hydroquinone
It should be noticed that, even when using a strong hydrogen
bonding coordinating solvent such as DMSO, the presence of sig-
nals IVa–IVc indicates that the intermolecular interaction between
QH2 and Q2− must be very strong. This effect resulted in the for-
mation of those signals during voltammetric titration experiments
of 1,4-benzoquinone (Q) with hydroquinone (QH2 ) (Fig. 6). The
voltammetric behaviour of 1,4-benzoquinone (Q) as a function of
several concentrations of hydroquinone (QH2 ) was carried out in
DMSO.
Fig. 6 (black curve) shows the peaks Ic–Ia and IIc–IIa, which
represent the classical behaviour of benzoquinone 2 mM in pure
DMSO. In the presence of 1 mM QH2 (red curve), signals IIc–IIa
decrease in intensity while the broad signal IVc–IVa appears at sim-
ilar potential values as the broad signal IVc–IVa observed in Fig. 5B.
This effect is magnified by increasing the concentration of QH2 up
to 2 mM (green curve). Even at this concentration conditions (1:1
relationship), a small fraction of the signals corresponding to the
free dianion Q2− (peaks IIc–IIa) are still observed, implying that the
formation of the complex between Q2− and QH2 is not 100% quan-
titative. Upon increasing even more the concentration of QH2 until
4 mM (blue curve), only the signals Ic–Ia and IVc–IVa are mainly
observed (Fig. 6B). This result confirms that the dianionic type quin-
hydrone complex can also be formed by direct interaction between
Q2− and QH2 . The high value for the association constant between
Fig. 6. Cyclic voltammetry of 1,4-benzoquinone 2 mM in the presence of different
concentrations of hydroquinone: (black) 0 mM, (red) 1 mM, (green) 2 mM, (blue)
4 mM; on glassy carbon electrode (3 mm ␾), in DMSO + 0.1 M n-Bu4 NPF6 at 0.1 Vs−1 .
(For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of the article.)
Q2− and QH2 is qualitatively manifested by the fact that intensity
of peaks IIc–IIa diminishes at the same time that peaks IVc–IVa
increase their current intensity, such as it was verified in a previous
study about the chloranil reduction in presence of several amides
[66]. As it was previously mentioned, the reason of this strong inter-
action must be related to the formation of two hydrogen bonds in
the ionic-neutral mode. The nature of such interaction is discussed
in the next section from the point of view of electronic structure cal-
culations. In this framework and considering the species depicted in
Scheme 1 the interconversion between the complexes [Q2− · · ·QH2 ]
and [QH− · · ·QH− ] was considered.
3.6. Electronic structure calculations of the complexes
[Q2− · · ·QH2 ] and [QH− · · ·QH− ]
In order to analyse the stability of the quinone
dianion–hydroquinone complex [Q2− · · ·QH2 ] and hydroquinone
monoanion dimer [QH− · · ·QH− ], the electronic structure cal-
culations using Density Functional Theory were performed for
the systems studied. For this purpose, four different function-
als were employed, specially to take into account the effect of
intermolecular hydrogen-bonding [67,68] and ␲–␲ interactions
within the structures proposed [69]. Full geometry optimization
of the structures for both complexes indicates the stability of a
face-to-face dimer, as suggested above (Fig. 7).
A collection of selected results from the geometric and energetic
analysis of the complexes is presented in Table 1. From the results
obtained, it is apparent that the use of the MPW1PW1 functional
leads to the lowest values of total energies for the series of opti-
mized structures. It should be noticed that this functional has been
used to analyse stability effects in dimers where ␲–␲ interactions
play a dominant role such as in benzene dimers [69]. However,
there is a slight shift between the planes of both aromatic rings
(Fig. 7, upper structures), and this shift diminishes the interaction
between the ␲ electrons of the rings. Therefore, most of the stabil-
ity effects should be addressed to the hydrogen bonding effects of
the OH terminal groups. In particular, the use of BHandHLYP func-
tional led to a significant low value of the HOMO level, compared
with the MPW1PW1 and PBE functional, the latter being known as
 P.D. Astudillo et al. / Electrochimica Acta 81 (2012) 197–204 203

Table 1
Selected geometric parameters and energies of the dimeric structures considered in
this work.

Dimer Etotal /kJ mol−1 EHOMO /eV r O H/nm r O· · ·H/nm

− −
[QH · · ·QH ] −2,007,358a 2.4847 0.09884 0.18808
−2,006,647b 2.5045 0.09894 0.18717
−2,006,676c 1.6904 0.09722 0.19895
−2,006,471d 0.2727 0.09886 0.18793
[Q2− · · ·QH2 ] −2,007,325a 3.0882 0.10556 0.15045
−2,006,617b 3.0831 0.10598 0.14910
−2,006,638c 2.5587 0.10156 0.16205
−2,006,437d 0.9099 0.10545 0.15106

Each line shows results from the different functionals employed.

a
MPW1PW1.
b
MPW1PBE.
c
BHandHLYP.
d
Long range corrected PBE.

that the PBE electron correlation parameters are required for a

Fig. 7. Optimized structures of (A) [QH− · · ·QH− ] and (B) [Q2− · · ·QH2 ] at the LC-
PBE/6-311 + +G(d,p) level. Upper figures represent views from H O· · ·H sides; lower
figures show lateral views of both dimers.
useful for accounting of hydrogen bonding effects. This effect is not
associated to significant changes in geometric parameters for the
optimized structures of both dimers, but suggests that increasing
the amount of Hartree–Fock exchange is relevant to indicate a more
stable structure, as expected for this type of polar interactions. This
correction effect has been addressed before in the analysis of reac-
tive trends in substituted quinone systems [28], though this was
relevant in single molecules. As this type of effects diminishes sig-
nificantly with the distance between the considered species, long
range corrections are necessary to account for this effect in the
total energy. For this purpose, the long range corrected functional
PBE (LC-PBE) was also employed, showing a significant decrease
in the HOMO value for both [QH− · · ·QH− ] and [Q2− · · ·QH2 ] com-
plexes (Table 1). It should also be noticed that hydrogen bonding
distances calculated with this functional are comparable with those
obtained with the hybrid MPW1PBE functional, thus suggesting
correct estimation of the electronic effects of this type of bond.
Considering the possibility of the fast interchange between both
[QH− · · ·QH− ] and [Q2− · · ·QH2 ] structures suggested through the
experimental study, an analysis of a potential energy surface (PES)
was performed by changing the distances between the OH bond
and the hydrogen bonding between the O− residue and the neigh-
bouring H atoms. Fig. 8 shows the contour lines of the constructed
PES with the LC-PBE functional along with the plot of the mini-
mum energies of the PES, from which activation parameters were
calculated.
With this analysis, a transition state can be identified, from
which activation parameters for the interconversion between
structures [QH− · · ·QH− ] and [Q2− · · ·QH2 ] were estimated. For
instance, an activation energy of 108.4 kJ mol−1 was determined for
converting structure [QH− · · ·QH− ] into [Q2− · · ·QH2 ], meanwhile,
for the opposite process, an activation energy of 28.4 kJ mol−1 was
found. Even though these theoretical results suggest that struc-
ture [QH− · · ·QH− ] is more stable than [Q2− · · ·QH2 ], the calculated
activation energies are lower than the thermal activation factor at
298.15 K (NA kB T ∼ 2480.2 kJ mol−1 ); thus, it is possible than with
the temperature at which the experimental data were obtained,
rapid thermal interconversion between both structures is occur-
ring.

Fig. 8. (A) Potential energy surface of the transition between structures [QH− · · ·QH− ] and [Q2− · · ·QH2 ] at the LC-PBE/6-311 + +G(d,p) level. (B) Variation of the reaction energy
along the minima of PES. In both figures, the position of conformers [QH− · · ·QH− ] and [Q2− · · ·QH2 ] are indicated.
204 P.D. Astudillo et al. / Electrochimica Acta 81 (2012) 197–204
4. Conclusions
The electrochemistry of the 1,4-benzoquinone and hydro-
quinone system in organic media was analysed. Using cyclic
voltammetry, it was found that the electrochemical behaviour of
quinone in the presence of small amounts of proton donors can-
not be explained in terms of the classical mechanisms of quinone
reduction, due to the fact that the anion QH− disproportionates into
a face-to-face dianionic quinhydrone associated complex stabilized
by strong intermolecular hydrogen bonds. It was demonstrated
that this complex can be formed by the reduction of benzoquinone
in either the presence of stoichiometric amounts of weak proton
donors or by half-deprotonation of hydroquinone, as also evaluated
by 1 H NMR experiments. Theoretical analysis of energetic barriers
for hydrogen transfers involved in the complexes formation indi-
cated that interconversion between [QH− · · ·QH− ] and [Q2− · · ·QH2 ]
species is possible, and that it could be driven by thermal effects
rather than thermodynamic stability.
Acknowledgements
P.D. Astudillo and D. Valencia acknowledge CONACyT for
their Ph.D. scholarships. M.A. González-Fuentes also acknowl-
edges CONACyT for a postdoctoral fellowship. C. Frontana thanks
CONACyT-México for support through project number 107037
(Fondo de Investigación Científica Básica SEP-CONACyT 2008).
References
[1] J.L. Cape, M.K. Bowman, D.M. Kramer, Phytochemistry 67 (2006) 1781.
[2] J.E.Q. Walker, Quarterly Reviews of Biophysics 25 (1992) 253.
[3] E.A. Hillard, F.C. de Abreu, F. Caxico, D.C. Ferreira, G. Melo, M.O.F. Jaouen, C.
Goulart, Amatore, Chemical Communications 23 (2008) 2612.
[4] J.Q. Chambers, in: S. Patai (Ed.), Chemistry of Quinonoid Compounds, vol. 2, Part
1, 1988, pp. 719–757.
[5] M. Kurosi, E. Begari, Molecules 15 (2010) 1531.
[6] J. Oldenburg, M. Marinova, C. Muller-Reible, M. Watzka, Vitamins & Hormones
78 (2008) 35.
[7] J.E. Sadler, Nature 427 (2004) 493.
[8] J. Hirst, Biochemical Journal 425 (2010) 327.
[9] A.D. Vinogradov, Biochimica et Biophysica Acta 1777 (2008) 729.
[10] M. Sarasate, Science 283 (1999) 1488.
[11] M.R. Gunner, J. Madeo, Z. Zhu, Journal of Bioenergetics and Biomembranes 40
(2008) 509.
[12] P. Joliot, A. Joliot, G. Johnson, Advances in Photosynthesis and Respiration 24
(2006) 639.
[13] U. Siggel, Bioelectrochemistry and Bioenergetics 3 (1976) 302.
[14] M. Hervás, J.A. Navarro, M.A. de la Rosa, Accounts of Chemical Research 36
(2003) 798.
[15] V.K. Tandon, R.V. Singh, D.B. Yadav, Bioorganic & Medicinal Chemistry Letters
14 (2004) 2901.
[16] S. Hayashi, H. Ueki, Y. Ueki, H. Aoki, K. Tanaka, J. Fujimoto, K. Katsukawa, M.
Mori, Chemical & Pharmaceutical Bulletin 11 (1963) 948.
[17] D.N. Singh, N. Verma, S. Raghuwanshi, P.K. Shukla, D.K. Kulshreshtha, Bioor-
ganic & Medicinal Chemistry Letters 16 (2006) 4512.
[18] G. Meazza, F.E. Dayan, D.E. Wedge, Journal of Agricultural and Food Chemistry
51 (2003) 3824.
[19] E.N. da Silva, T.T. Guimaraes, R.F.S. Menna-Barreto, M.C.F.R. Pinto, C.A. de
Simone, C. Pessoa, B.C. Cavalcanti, J.R. Sabino, C.K.Z. Andrade, M.O.F. Goulart,
S.L. de Castro, A.V. Pinto, Bioorganic & Medicinal Chemistry 18 (2010) 3224.
[20] K.A.L. Ribeiro, C. Monteiro de Carvalho, M.T. Molina, E.P. Lima, E. Lopez-
Montero, J.R.M. Reys, M.B. Farias de Oliveira, A.V. Pinto, A.E.G. Santana, M.O.F.
Goulart, Acta Tropica 111 (2009) 44.
[21] E.N. da Silva, C.F. de Deus, B.C. Cavalcanti, C. Pessoa, L.V. Costa-Lotufo, R.C. Mon-
tenegro, M.O. de Moraes, M.C.F.R. Pinto, C.A. de Simone, V.F. Ferreira, M.O.F.
Goulart, C.K.Z. Andrade, A.V. Pinto, Journal of Medicinal Chemistry 53 (2010)
504.
[22] Y. Chen, L. Hu, Medicinal Research Reviews 29 (2009) 29.
[23] S.I. Bailey, I.M. Ritchie, Electrochimica Acta 30 (1985) 3.
[24] M. Quan, D. Sanchez, M.F. Wasylkiw, D.K. Smith, Journal of the American Chem-
ical Society 129 (2007) 12847.
[25] M. Aguilar-Martínez, N.A. Macías-Ruvalcaba, J.A. Bautista-Martínez, M. Gómez,
F.J. González, I. González, Current Organic Chemistry 8 (2004) 1721.
[26] B.R. Eggins, J.Q. Chambers, Journal of the Electrochemical Society 11 (1970)
186.
[27] P. Zuman, Substituent Effects in Organic Polarography, Plenum Press, NY, 1967.
[28] C. Frontana, A. Vazquez-Mayagoitia, J. Garza, R. Vargas, I. González, Journal of
Physical Chemistry A 110 (2006) 9411.
[29] M. Aguilar-Martinez, G. Cuevas, M. Jimenez-Estrada, I. González, B. Lotina-
Hennsen, N. Macias-Ruvalcaba, Journal of Organic Chemistry 64 (1999) 3684.
[30] M. Gómez, F.J. González, I. González, Journal of Electroanalytical Chemistry 578
(2005) 193.
[31] C. Frontana, I. Gonzalez, Journal of the Brazilian Chemical Society 16 (2005)
299.
[32] N.A. Macias, D.H. Evans, Journal of Physical Chemistry C 114 (2010) 1285.
[33] L.S. Hernández-Muñoz, M. Gómez, F.J. González, I. González, C. Frontana,
Organic & Biomolecular Chemistry 7 (2009) 1896.
[34] M. Shamsipur, A. Siroueinejad, B. Hemmateenejad, A. Abbaspour, H. Sharghi, K.
Alizadeh, S. Arshadi, Journal of Electroanalytical Chemistry 600 (2007) 345.
[35] C. Ruessel, W. Jaenicke, Journal of Electroanalytical Chemistry 199 (1986) 139.
[36] B. Uno, N. Okumura, M. Goto, K. Kano, Journal of Organic Chemistry 65 (2000)
1448.
[37] N. Okumura, B. Uno, Bulletin of the Chemical Society of Japan 72 (1999) 1213.
[38] B.R. Clark, D.H. Evans, Journal of Electroanalytical Chemistry 69 (1976) 181.
[39] C. Frontana, B. Frontana-Uribe, I. González, Journal of Electroanalytical Chem-
istry 573 (2004) 307.
[40] S. Klod, L. Dunsch, Magnetic Resonance in Chemistry 49 (2011) 725.
[41] T. Hoshino, M. Oyama, S. Okazaki, Journal of Electroanalytical Chemistry 472
(1999) 91.
[42] H. Park, M. Oyama, Electroanalysis 14 (2002) 1269.
[43] D.H. Evans, D.A. Griffith, Journal of Electroanalytical Chemistry 136 (1982) 149.
[44] N. Gupta, H. Linschitz, Journal of the American Chemical Society 119 (1997)
6384.
[45] B. Uno, A. Kawabata, K. Kano, Chemistry Letters 6 (1992) 1017.
[46] M. Gómez, F.J. González, I. Gonzalez, Journal of the Electrochemical Society 150
(2003) E527.
[47] S. Ahmed, A.Y. Khan, R. Qureshi, M.S. Subhani, Russian Journal of Electrochem-
istry 43 (2007) 811.
[48] B. Uno, N. Okumura, K. Seto, Journal of Physical Chemistry A 104 (2000) 3064.
[49] P.D. Astudillo, J. Tiburcio, F.J. González, Journal of Electroanalytical Chemistry
604 (2007) 57.
[50] C. Costentin, Chemical Reviews 108 (2008) 2145.
[51] M. Salas, M. Gómez, F.J. González, B. Gordillo, Journal of Electroanalytical Chem-
istry 543 (2003) 73.
[52] F. D’Souza, G.R. Deviprasad, Journal of Organic Chemistry 66 (2001) 4601.
[53] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro,
M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, T. Keith, R.
Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J.
Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken,
C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R.
Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski,
G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B.
Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09 Revision B.01, Gaussian,
Inc, Wallingford, CT, 2010.
[54] Used as defined in Gaussian 09 Manual: 0.5EXHF + 0.5EXLSDA + 0.5EXBecke88
+ ECLYP.
[55] C. Adamo, V. Barone, Journal of Chemical Physics 108 (1998) 664.
[56] A.D. Becke, Journal of Chemical Physics 104 (1996) 1040.
[57] Y. Tawada, T. Tsuneda, S. Yanagisawa, T. Yanai, K. Hirao, Journal of Chemical
Physics 120 (2004) 8425.
[58] O.A. Vydrov, G.E. Scuseria, Journal of Chemical Physics 125 (2006) 234109.
[59] O.A. Vydrov, J. Heyd, A. Krukau, G.E. Scuseria, Journal of Chemical Physics 125
(2006) 074106.
[60] O.A. Vydrov, G.E. Scuseria, J.P. Perdew, Journal of Chemical Physics 126 (2007)
154109.
[61] C. Amatore, J.-M. Savéant, Journal of Electroanalytical Chemistry 85 (1977) 27.
[62] C.L. Perrin, J.B. Nielson, Annual Review of Physical Chemistry 48 (1997)
511.
[63] L.A. Clare, L.E. Rojas-Sligh, S.M. Maciejewski, K. Kangas, J.E. Woods, L.J. Deiner,
A. Cooksy, D.K. Smith, Journal of Physical Chemistry C 114 (2010) 8938.
[64] D.P. Valencia, F.J. González, Electrochemistry Communications 13 (2011) 129.
[65] J.H. Wilford, M.D. Archer, Journal of Electroanalytical Chemistry 190 (1985)
271.
[66] M. Gómez, C.Z. Gómez-Castro, I.I. Padilla-Martínez, F.J. Martínez-Martínez, F.J.
González, Journal of Electroanalytical Chemistry 567 (2004) 269.
[67] R. Li, K. Hongwei, F. Gang, X. Xin, Y. Yijing, Journal of Chemical Theory and
Computation 5 (2009) 86.
[68] N.A. Benedek, K. Latham, I.K. Snook, I. Yarovsky, Journal of Physical Chemistry
B 110 (2006) 19605.
[69] M.J. González-Moa, M. Mandado, R.A. Mosquera, Journal of Physical Chemistry
A 111 (2007) 1998.