Polyhedron 21 (2002) 2137 /2142

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2-Mercaptobenzoxazole pentacyanoferrate(II/III) complexes* /

kinetics of formation, substitution and the thermodynamic cycle

Juciane B. Luiz a, G. Jeffery Leigh b, Fábio S. Nunes a,*
a
Departamento de Quı́mica, Centro Politécnico, Universidade Federal do Paraná, C.P. 19081, 81531-990 Curitiba, PR, Brazil
b
School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton BN1 9QJ, UK

Received 25 February 2002; accepted 15 July 2002

Abstract

The kinetics of substitution and formation of [FeII/III(CN)5(bzoxsh)]3/2 (bzoxsh /2-mercaptobenzoxazole) complexes were
investigated in a MeOH/H2O (75:25%) solvent mixture at m /1.00 NaClO4 mol l 1. The rates of bzoxsh dissociation for the FeII/III
ions, kdII /3.7/10 4 and kdIII /4.5 /10 3 s 1 at 25 8C, were determined through conventional kinetics in the presence of a
large excess (102 /103-fold) of the attacking reagents (L /dimethylsulfoxide (dmso), pyridine (py) and N -methylpyrazinium) over
the iron complexes. Second-order rate constants, kf II /2.9 /102 and kf III /3.9 /106 dm3 mol 1 s 1 and equilibrium constants,
Kf II /7.8 /105 and Kf III /8.6 /108 dm3 mol 1, were also calculated using the construction of a thermodynamic cycle. The formal
reduction potential of the FeIII/FeII complexes were determined as Efbzoxsh /0.19 V versus EPH. Activation parameters for the
dissociation reactions of [FeIII(CN)5(bzoxsh)]2 were found with DS# //11.4 J K 1 mol 1 and DH# /93.3 kJ mol 1. Specific
rate constant for the dissociation of [FeIII(CN)5(L)]2 , L/dmso and py, were obtained as 2.5/10 5 and 1.5 /10 5 s 1,
respectively. The kinetic and thermodynamic stabilities of the complexes are discussed and correlated with the metal
/ligand bond
type and the electronic properties of the ligands.
# 2002 Elsevier Science Ltd. All rights reserved.

Keywords: 2-Mercaptobenzoxazole; Pentacyanoferrate; Kinetics; Equilibrium constants; Electrochemistry

1. Introduction excellent contributions to this field, and in comparison

Many of the sulfur-donor ligands in biology have
more than one functional group capable of coordination
to transition metal ions [1]. The interest in reactions
between multifunctional ligands and the pentacyanofer-
rate ion is due to the fact that [Fe(CN)5]3/2 coordi-
nates only one additional ligand (L) and has been used
to probe the binding affinity of specific groups towards
iron [2]. The properties of the products,
[Fe(CN)5L]2/3, are strongly dependent on the nature
of L. Pentacyanoferrate(II) shows a high affinity for
sulfoxides [3], thioethers [4] and N- heterocycles [5a] such
as imidazole [5b]. Stable complexes with S -containing
aminoacids have also been reported [6]. In spite of the
with the N- donors, few sulfur-ligands have been studied.
There is extensive information gathered about ligand
substitution reactions of pentacyanoferrate complexes
[2,7] and the subject is still given considerable attention
[2a]. Contrasting with [FeII(CN)5L]3, little is known
about the interaction of the pentacyanoferrate(III) ion
with S -donor. Continuing our studies on the reactivity
of transition metal complexes of bio-inorganic interest
[8], here we report the kinetic and thermodynamic
properties of complexes [Fe(CN)5(bzoxsh)]2/3
(bzoxsh/2-mercaptobenzoxazole, Fig. 1), and explore
the competition between the donor groups in 2-mercap-

* Corresponding author. Tel.: /55-41-361-3180; fax: /55-41-361-

3186
E-mail address: fsnunes@quimica.ufpr.br (F.S. Nunes). Fig. 1. Ligand 2-mercaptobenzoxazole, bzoxsh.

0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 1 7 8 - 6
2138 J.B. Luiz et al. / Polyhedron 21 (2002) 2137 /2142
tobenzoxazol. This is an unsaturated heterocycle which
exists both in solid and in polar solution in the thione
tautomeric form with a protonated N-atom [9a,10].
Bzoxsh is structurally related to biologically important
bases and several transition-metal complexes have been
described in the literature [9].
2. Experimental
2.1. Physical measurements and instrumentation
Ligand dissociation reactions were followed through
conventional kinetics using a Hewlett-Packard Model
8452A diode-array spectrophotometer in MeOH/H2O
(75:25%) thermostated solutions. All experiments were
performed under pseudo-first-order conditions and the
reactions were monitored for 5 /6 half-lives. Dissocia-
tion of the substituted pentacyanoferrates takes place to
a very small extent at room temperature. The kinetics
were investigated in the presence of the compounds L /
dimethylsulfoxide (dmso), pyridine (py) for FeIII and N -
methylpyrazinium for FeII. These have strong affinities
for pentacyanoferrate group, allowing the dissociation
reactions to be safely followed [3,5a]. The rates of
substitution were studied as a function of 7/10 different
concentrations of L at a fixed bzoxsh concentration.
First-order rate constants were determined by four
different mathematical methods: least-squares or the
infinite absorbance method, Guggenheim, Kezdy /Swin-
bourne and a non-linear fitting [12], with excellent result
agreement. Second-order rate constants were calculated
from literature data (for FeII) and from the thermo-
dynamic cycle presented in this work. Temperature
dependence of the rate dissociation constants was
studied in the range of 10/30 8C.
Cyclic voltammetry measurements were carried out
with a Princeton Applied Research Potentiostat model
273A. A Pt disc electrode was employed for the
measurements at an ionic concentration of 0.5 mol
dm 3 kept constant with tetrabutylammonium tetra-
fluoroborate. A Ag/AgNO3 ([Ag ]/0.01 mol dm 3 in
an MeCN solution of But4 NBF4 0.1 mol dm 3) along
with a Pt wire were used as reference and auxiliary
electrodes, respectively. Typical experiments were con-
ducted with a 2.5 /10 3 mol dm 3 complex concen-
tration in MeOH/H2O (75:25%) solutions at ambient
temperature.
2.2. Materials
Na3[Fe(CN)5NH3] ×/3H2O was prepared from sodium
nitroprusside as described in the literature [11]. The
yellow product was stored in the dark at /15 8C. Anal .
Calc. for Na3[Fe(CN)5NH3] ×/3H2O: C, 18.4; H, 2.8; N,
25.8. Found: C, 18.0; H, 2.1; N, 24.6%.
The purity of the 2-mercaptobenzoxazole (Aldrich)
was confirmed by elemental analysis. Anal . Calc. for
C7H5NOS: C, 55.6; H, 3.3; N, 9.3. Found: C, 56.1; H,
3.3; N, 8.9%.
Solutions of the aquapentacyanoferrate(II) complex
were always freshly prepared using Schlenk techniques.
Na3[Fe(CN)5NH3]×/3H2O was dissolved in dinitrogen-
saturated water, mixed with three parts of MeOH (to
give a total iron concentration of 1 /5 /10 4 mol
dm 3) and enough sodium perchlorate to keep the
ionic strength at 1.00 mol dm 3. Solid 2-mercaptoben-
zoxazole (bzoxsh) was always dissolved in excess (20-
fold) to avoid competing reactions with small amounts
of free NH3 coming from the starting material.
Solutions of the aquapentacyanoferrate(III) complex
were also freshly prepared by oxidizing
[FeII(CN)5(H2O)]3 (obtained by dissolving the ammine
complex in water) with PbO2 in dinitrogen-saturated
water. The excess of PbO2 was filtered off and three
volumes of MeOH were added. After correction of the
ionic strength, solid bzoxsh was added, resulting in a
clear deep-green solution.
3. Results and discussion
Typical spectral changes for the reaction of
[FeIII(CN)5(bzoxsh)]2 with dmso and of
[FeII(CN)5(bzoxsh)]3 with N- methylpyrazinium are
illustrated in Fig. 2. The concentrations used gave
well-defined and reproducible first-order kinetic plots.
Dmso is suitable because it forms a very stable and
colorless complex with pentacyanoferrate(III) [3] and
the reaction was studied following the decay of the band
of the reactant at 706 nm. The same procedure was
applied when pyridine was the attacking reagent as the
[FeIII(CN)5(py)]2 complex is faintly yellow and ab-
sorbs at 410 nm. For the dissociation reactions involving
FeII, the formation of the blue [FeII(CN)5(N-
methylpyrazinium)]2 was monitored at 690 nm. The
dissociation kinetics exhibited good pseudo-first-order
behavior during at least two half-lives, with the attack-
ing L always present in large excess over the iron
complex (102 /103-fold).
According to the general mechanism for the dissocia-
tion reactions in pentacyanoferrate complexes [5a] we
can write:
kd
[FeIII=II (CN)5 (bzoxsh)]2=3 X [FeIII=II (CN)5 (H2 O)]2=3
kf
bzoxsh
kL
[FeIII=II (CN)5 (H2 O)]2=3 L X [FeIII=II (CN)5 (L)]2=3
kL
H2 O
where the loss of bzoxsh is the rate-determining step.
 J.B. Luiz et al. / Polyhedron 21 (2002) 2137 /2142
Fig. 2. UV /Vis spectra of [FeIII(CN)5(bzoxsh)]2 (top) and
[FeII(CN)5(N -methylpyrazinium)]2 in MeOH/H2O 75:25 (v/v); Inset
shows typical first-order kinetic curves: scatter, experimental data; line,
non-linear first-order exponential fit. Top shows the absorbance decay
of the 706 nm band typical of [FeIII(CN)5(bzoxsh)]2 after reaction
with dmso; Bottom shows the increase of the 690 nm band when
[FeII(CN)5(bzoxsh)]3 reacts with N -methylpyrazinium.
Assuming a steady-state approximation for
[Fe(CN)5(H2O)]2/3 the observed rate constant and its
reciprocal form (if k L
/kd) are given by Eqs. (1) and
(2):
kf kL [bzoxsh]  kL kd [L]
kobs 
kf [bzoxsh]  kL [L]
1 kf [bzoxsh] 1
 
kobs kL kd [L] kd
The expression (Eq. (1)) is coherent with the saturation
curve of kobs versus L and Eq. (2) with the linear
behavior of the reciprocal form as seen in Fig. 3. Since
the rates of formation of [Fe(CN)5L]3 are completely
independent of the nature of the entering ligand, as
expected for a limiting SN1 mechanism, we calculated a
medium value of kf II /290 dm3 mol 1 s 1 from
published results for neutral ligands at the same ionic
strength. kf II and (L) used for calculation were: 240
(dmso), 212 (imidazole), 184 (histidine) [6], 354 (4-
picoline), 365 (pyridine), 295 (isonicotinamide) and 380
(pyrazine) [3]. The stability constant Kf II was calculated
as kf II/kdII from the formation and dissociation reac-
tions. Kf III was calculated from the measured electro-
chemical potentials and the following redox cycle:
2139
Fig. 3. Plot of kobs versus attacking ligand concentration, showing rate
saturation. Top: reaction of [FeIII(CN)5(bzoxsh)]2 with dmso.
Bottom: [FeII(CN)5(bzoxsh)]3 reacts with N -methylpyrazinium. Inset
shows double reciprocals for determination of kd.
(1)
(2)
where Kf III /Kf II{exp[(nF/RT )(Efbzoxsh/EfH2O)]} 1.
The results for bzoxsh are similar to those described
for other neutral ligands. This holds for kf II (240 /400
dm3 mol 1 s 1) and Kf II (102 /106 dm3 mol 1) [3,5a,6].
Kf III is out of the range of 10 2 /106 dm3 mol 1 and this
is consistent with the lower limit of the formal reduction
potential, Efbzoxsh (Table 1). The relative strength of the
Fe
/L bond can be related with the basicity of L as
suggested by Eldik et al. [13]. The higher the sigma-
donor capacity of L the lower the lability of the Fe
/L
bond. However, pKa values represent only the sigma
part of metal /ligand interactions. As can be seen from
Table 1, the dissociation constants (kd) are not much
sensitive to large variations of pKa (compare, for
example pyrazine with histidine). This can be explained
 2140
Table 1
Kinetic and thermodynamic data for [Fe(CN)5L]2/3 complexes. The entries are in order of decreasing formal reduction potentials, EfL

pKa kdII (s 1) kdIII (s 1) kf II (mol 1 s 1) kf III (mol 1 s 1) I (mol dm 3) Kf II (dm3 mol 1) Kf III (dm3 mol 1) EfL a

J.B. Luiz et al. / Polyhedron 21 (2002) 2137 /2142

L Donor group Reference
at 25 8C at 25 8C at 25 8C at 25 8C
f
Dmso S O 7.5 10 5 2.5 10 5 2.4 102 9.3 10 7 1.00 LiClO4 4.9 106 3.7 10 2 850 [3,6]
e
Pyrazinium C N 0.6 4.2 10 4 3.80 102 e
1.00 LiClO4 1.9 106 b
1.7 103 550 [3,5] a[6]
e
Isonicotinamide C N 3.7 7.3 10 4 2.95 102 e
1.00 LiClO4 8.2 105 b
5.2 103 500 [3,5] a[6]
5 f
Pyridinium C N 5.3 1.1 10 3 1.5 10 3.65 102 1.4 10 1
1.00 LiClO4 4.6 105 b
9.4 103 470 [3,5] a[6]
e
Histidine C N 6.1 5.3 10 4 3.20 102 e
0.100 LiClO4 5.9 105 1.1 106 355 [6]
e
Imidazole C N 7.1 1.3 10 3 2.4 102 e
0.100 LiClO4 1.8 105 5.8 105 340 [6]
2-mpy c C S 1.8 1.7 10 2 e
2.85 102 e
0.1 KCl 1.6 104 6.4 105 272 [5c]
Bzoxsh C S 5.1 3.7 10 4 4.5 10 3
2.9 102 3.9 106 1.00 NaClO4 7.8 105 8.6 108 190 f

mtr d C S 4.6 10 4 e
3.0 e
0.100 NaClO4 1.5 104 e e
[14]
e e e e e e
1,4-Dithiane R
S
R 5.6 10 4 0.1 LiClO4 [4b]
a
mV vs EPH, the values refer to the FeIIIe  X FeII reversible process.
b
Calculated from Kf II and redox potentials.
c
2-Mercaptopyridine.
d
3-Mercapto-1,2,4-triazole.
e
Not determined
f
This work.
 J.B. Luiz et al. / Polyhedron 21 (2002) 2137 /2142
Table 2
Temperature dependence of the rate constant for the dissociation of
[FeIII(CN)5(bzoxsh)]2
Temperature (8C) 104 kd (s1)
10 5.69
15 11.5
20 22.9
25 45.6
30 81.4
if we consider that both the s-donor and back-bonding
have the same effect on the substitution rate of L in a
pentacyanoferrate complex, making it more inert. Back-
bonding is bigger for less basic L. The
[FeIII(CN)5(bzoxsh)]2 complex is approximately 10
times more labile than the reduced form, a result
consistent with the lack of back-bonding for the FeIII
ion. The same argument can be used to explain the
higher observed lability of [FeIII(CN)5(dmso)]2 over
[FeII(CN)5(dmso)]3 (kdIII /2.5 /104 s 1 [this work]
versus 7.5 /105 s 1 [3]). In this case preferential p-
back-bonding stabilization of the FeII /dmso complex is
an important factor being also probably responsible also
for the high value of Kf II (Table 1).
Interestingly, bzoxsh appears to behave as a fair p-
acceptor as well as a strong s-donor ligand, as it
stabilizes both oxidation states of pentacyanoferrate
complexes. This bonding behavior is also observed for
histidine, imidazole and 2-mercaptopyridine (2-mpy).
Considering the thermodynamic stability of the com-
plexes, although both the pKa values of bzoxsh (S
/H
group) and pyridine are similar, bzoxsh is a weaker p-
acceptor, consistent with the significantly lower value of
Efbzoxsh and the high value of Kf III. Conversely, pyridine
shows greater stabilization of the pentacyanoferrate(II)
ion over the oxidized form (Table 1).
The dissociation constants observed for
[FeIII(CN)5(py)]2 and [FeII(CN)5(py)]3 are 1.5 /
105 [this work] and 1.1 /103 s 1 [5a], respectively,
showing that pyridine prefers the hard FeIII ion, the
back-bonding interactions having less importance here.
Fig. 4. Eyring plot for the reaction of [FeIII(CN)5(bzoxsh)]2 with
pyridine.
2141
The effect is very pronounced, [FeIII(CN)5(py)]2 being
much more inert than its reduced form.
If we compare the kdIII values for the [FeIII(CN)5L]2
complexes, we can establish the following order of
increasing lability: py (1.5 /105 s 1)B/dmso (2.5 /
104 s1) B/bzoxsh (4.5 /103 s 1). This result sug-
gests that bzoxsh is bound to FeIII through the soft
sulfur atom. If the coordination were through the
nitrogen atom, we would expect the complex to be as
inert that of pyridine. When kdII values are compared,
the order is dmso (7.5 /105 s 1)B/bzoxsh (3.7 /104
s 1)B/py (1.1 /103 s 1), emphasizing the importance
of back-bonding in the stabilization of these FeII
compounds.
Completing the investigation of the less studied
[FeIII(CN)5L]n series, activation parameters for the
dissociation reaction of [FeIII(CN)5(bzoxsh)]2 were
determined (Fig. 4 and Table 2). They are DS# /
/11.4 J K 1 mol 1 and DH# /93.3 kJ mol 1, typical
of a dissociative type mechanism.
We hope that these results will help fill the gap in the
kinetic data available for pentacyanoferrate(III).
Acknowledgements
This work was supported by Brazilian PRONEX
Program (Contract Number 41.96.0884.00), whose help
we gratefully acknowledge. We thank Professor Henri-
que Eisi Toma (Institute of Chemistry */USP, Brasil)
for the valuable suggestions. J.B.L. and F.S.N. also
thank UFPR and Brazilian Research Council (CNPq)
for research fellowships.
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