Intramolecular Hydrogen Bonding/Selfprotonation Processes

Modulated by the Substituent Effect in Hydroxyl-substituted

Naphthoquinones
Teresita Maldonando, Eduardo Martnez-Gonzlez, Carlos Frontana

Centro de Investigacin y Desarrollo Tecnolgico en Electroqumica (CIDETEQ), Parque Tecnolgico Sanfandila, Pedro Escobedo, Quertaro, A.P. 064.
C.P. 76703, Mxico.
cfrontana@cideteq.mx

Introduction

Electron transfer reactions of quinone compounds are essential processes in living systems for energy conversion, where the properties of the
electrogenerated reactive intermediates (either a semiquinone or a dianion), are related to their final biological activity [1-6]. Quinone reactivity
depends on the nature of the substituents present, this substituent effect was parameterized using a variation of the classical Hammett model by
Zuman, leading to an approach which relates the substituent effect with experimental standard reduction or oxidation potentials [7]. However, in 1,4naphthoquinone systems containing hydroxyl substituents, some compounds showed significant deviations from the expected Hammett-Zuman
relationship [8], a change in the mechanism of electron transfer is suggested, although no further discussion was given, which could be relevant for
fully understanding the reactivity of this family of quinones.
It is now known that Hydroxyl-substituted naphthoquinones experimental behavior does not follow the quinone typical two monoelectronic reversible
charge transfer processes, instead it follows both electron transfer processes and coupled chemical father-son reactions called selfprotonation (SP).
Therefore, in this work, an electrochemical and spectroelectrochemical-Electron Spin Resonance (E-ESR) study of the electron transfer processes
involved in a series of hydroxyl-substituted 1,4-naphthoquinone are presented (Scheme 1). Results are discussed considering the relative positions of
the hydroxyl substituents and also by evaluating possible coupling between electron and proton transfer reactions.

Scheme 1. Structures of the studied

hydroxyl substituted 1,4naphthoquinone compounds.

Experimental
The general methodology is described in two major stages:
ESR spectra were recorded in the X band (9.85 GHz), using a Brucker ELEXSYS 500
I. Substituent effects by hydroxyl groups in the electrochemical behaviour of 1,4- instrument with a rectangular TE102 cavity. A commercially available spectroelectrochemical
naphthoquinones.
cell (Wilmad) was used. A platinum mesh (0.2 cm 2) working electrode was introduced in the
II. Spectroelectrochemical-Electron Spin Resonance (ESR) study of hydroxyquinones.
flat path of the cell. Another platinum wire was used as counter electrode (2.5 cm 2). A silver
Electrochemical experiments were performed using solutions 1 mM of 1,4-naphthoquinones. wire covered with silver chloride was employed as a pseudoreference electrode. Potential
Anhydrous acetonitrile (CH3CN), and tetrabutylammonium hexafluorophosphate (Bu 4NPF6) sweep control was performed with an AUTOLAB 302N potentiostat.
were used as solvent and supporting electrolyte, respectively. Cyclic voltammetry PEST WinSim free software version 0.96 was used to perform ESR spectra simulation, to
experiments were performed using PGSTAT AUTOLAB 302N potentiostat (: 0.1-10 Vs-1 and compare with the experimental ones.
Ru: 60-210 ). A glassy carbon disk electrode (0.07 cm 2) was used as a working electrode. A Electronic structure calculations were performed with Gaussian 09W, revision B.01, using the
non-aqueous electrode Ag|Ag+ and a platinum wire, were used as the reference and auxiliary density functional theory approach and the BHandHLYP functional with a 6-311++G(2d,2p)
electrodes, respectively. The potential values obtained are referred to the basis set [10]. Optimized structures were obtained, considering the solvent effect by the
ferrocene/ferricinium (Fc/Fc+) couple as recommended by IUPAC [9]. Tetrabutylammonium Marenich, Cramer, and Truhlar model [11].
hydroxide 1 mol L-1 (nBu4NOH) was used to deprotonate the correspondingResults
quinone. Inert
and Discussion
atmosphere was maintained by saturation with high-purity nitrogen at room temperature
I. Substituent
effects by hydroxyl
(approx.
20C).
The experimentally determined slopes were lower than 60
mV dec-1, therefore, the observed electrochemical behaviour
groups in the electrochemical
is related to the presence of a coupled chemical reaction
behaviour
of
1,4-naphthoquinones
Compounds 1 and 2 (Fig. 1) undergo a two-step sequential which occurs after the first electron uptake. These results
reduction process, where both electrochemical reactions are are consistent with the presence of a selfprotonation
reversible. This behaviour is the one typically observed for process [12, 19-20], and its reaction sequence is depicted as
the reduction of quinones in aprotic media, and is related to follows,
the transformation of the quinone into a semiquinone (at
(3)
peak Ic), and the reduction of the latter intermediate at peak
(4)
(5)
IIc into a dianion species, as depicted in the following
or
chemical equations,
(5)
(1)
(6)
Fig. 4. ESR spectrum of the dianion radical of (A) 2-hydroxy-1,4naphthoquinone 3, (B) 2,3-dihydroxy-1,4-naphthoquinone 4, (C) 2,3,5(2)
(7)
trihydroxy-1,4-naphthoquinone 5 and (D) 2,3,5,8-tetrahydroxy-1,4The observed oxidation steps are related to the generated
Coupling Constants
naphthoquinone 6, Hyperfine
electrogenerated
at -1.8 V vs Fc/Fc
Compoun
hydroquinones or (). The chemically generated anion (), is
a1 / G
a2 / G
a3 (G)
a4 (G)
a5 (G)
d
(G)
in turn reduced at peak IIc, in a quasi-reversible process,
1.42
0.49
0.25
0.1
2.34 (3.58)
generating a dianion radical species,
3
(2.18) (1.82) (0.89) (0.79)
0.04
H-6
H-8
H-5
H-3
H-7

(8)
0.42
1.22
(1.90)
T
This proposal was verified by performing electrochemical
(0.2)T
4

0.05
experiments in the presence of nBu 4NOH, as a
H-5,
H-6, H-7
H-8
deprotonating agent [19, 21-23] (Fig. 3).

Fig. 1. Cyclic voltammograms of 1 mM (A) 1,4-naphthoquinone 1 and (B)

5,8-dihydroxy-1,4-naphthoquinone 2. : 0.1 V s-1.

In Fig. 2, compounds 3 to 6 show a lack of reversible

behaviour in the first electron transfer step, as evaluated
from the difference in peak potential values between peaks Ic
and Ia (EIc-Ia), which is higher than 0.06 V. In all the
compounds a second reversible electron transfer was
observed.

Fig 3. Cyclic voltammograms of (A) 2-hydroxy-1,4-naphthoquinone 3;

(B) 2,3-dihydroxy-1,4-naphthoquinone 4, (C) 2,3,5-trihydroxy-1,4naphthoquinone 5 and (D) 2,3,5,8-tetrahydroxy-1,4-naphthoquinone 6,
in the presence (black lines) and absence (dashed lines) of nBu4NOH. :
0.1 V s-1. Equivalents employed for each deprotonation experiment were
(A) 1 eq, (B, C and D) 2 eq.

Fig. 2. Cyclic voltammograms of (A) 2-hydroxy-1,4-naphthoquinone 3; (B)

E 4;
/ 2,3,5-trihydroxy-1,4EIIc-IIa/
Compou
Ic-Ia(C)
0
2,3-dihydroxy-1,4-naphthoquinone
EIc / V EIa /V
E3/V*
nd 5 and (D) 2,3,5,8-tetrahydroxy-1,4-naphthoquinone
V
V
naphthoquinone
6, :
-1
0.1 V s0.07
.
1
-1.11 -1.04
-1.70
0.08
2 Data -0.85
0.06 analysis
-1.38of the
0.07
Table 1.
from the-0.78
voltammetric
studied
3
-0.85 -0.69
0.17
-1.76
0.11+
hydroxyquinones.
Data are presented
in V vs Fc/Fc

4
-0.94
5
-0.91
*
6
-0.93
E30=(EpIIc+EpIIa)2

-0.73
-0.78
-0.84

0.21
0.14
0.09

-1.71
-1.40
-1.46

0.10
0.17
0.09

In order to establish if the irreversible behaviour is either

chemically orCompoun
electrochemically
experiments at
Slope /mVcontrolled,
2
Rcompounds 3 to 6
-1
different scan rates
were
performed
for
d
dec
[12]. Upon comparing
EIc-36
values
their corresponding
3
1 with0.993
4
log
1 v slopes
0.988where obtained.
scan rates, the following
Ep-36
vs
Ic
5
6

-30 1
-2 0.4

0.986
0.669

Table 2. Experimentally determined slopes of the EpIc = f(log ) function

II. Spectroelectrochemical-Electron
Spin Resonance (ESR) study of
hydroxyquinones

As expected from the selfprotonation sequence described, a

lack of stable radical signals was observed upon studying
the spectroscopic response at applied potential values in the
potential region between signals Ic and IIc. On the other
hand, stable radical species were generated by applying
potential values more negative than the corresponding
peaks IIc, related to the reduction of deprotonated species
of the original compounds.
In Table 3, values for the hyperfine coupling constants (a)
from the experimental spectra patterns are shown, which
were determined by simulating the ESR spectrum (Fig. 4).
Electronic structure calculation was performed to assign a
values to their corresponding spin density, showing that the
highest hyperfine coupling with H atoms is located at
positions C-6 and C-8 for compound 3, C-6 and C-7 for
compounds 4 and 6; while for compound 5 only one HFCC
value was obtained. This pattern is significantly different
from the one expected, due to the lack of symmetry

2.41(3.3,
1.31, 0.63,
0.22) OH-5,
H-6, H-7, H8

2.28T (3.14)
H-6, H-7

0.56T
(0.25)
H-5,
H-8

Conclusions

0.14

0.05

Electrochemical behaviour is dependant on the relative

hydroxyl-substituent positions in the molecular structure.
When hydroxyl-substituents are present in positions C-2
and C-3, a selfprotonation process occurs.
The electrogenerated dianion/trianaion radicals show that
an intramolecular hydrogen bonding has a significant
effect both in the spin density distribution and the
required energy for the formation of these radical species.
The difference observed in the Ep Ic vs log function slope
for compound 6 suggests that, for this compound, the
proton transfer step does not occur as a single, but as a
two-step sequence, where an hydrogen bonded adduct
could be present as a stable intermediate.

Acknowledgements

T. Maldonado and E. Martnez-Gonzlez thank CONACyTMexico for economical support for their graduate studies. C.
Frontana thanks CONACyT for financial support through
Project 207688 (Joint Project between CONACyT-Mexico and
BMF).

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