ISSN 1061-9348, Journal of Analytical Chemistry, 2008, Vol. 63, No. 7, pp. 680–683. © Pleiades Publishing, Ltd., 2008.

Original Russian Text © M.S. Chernov’yants, I.V. Burykin, N.V. Aleshina, 2008, published in Zhurnal Analiticheskoi Khimii, 2008, Vol. 63, No. 7, pp. 745–748.

ARTICLES

Electrophoretic and Spectrophotometric Determination

of Triiodides of Sulfur-Containing Organic Cations
M. S. Chernov’yants, I. V. Burykin, and N. V. Aleshina
Department of Chemistry, South Federal University, ul. Zorge 7, Rostov-on-Don, 344090 Russia
Received May 21, 2007; in final form, October 19, 2007

Abstract—Trimethylsulfonium triiodide (I) and p-xylylene-bis-(tetrahydrothiophenium) triiodide (II) were

identified and determined by capillary electrophoresis with the resolution Rs = 4.86 using an unmodified quartz
capillary. The procedure ensures the determination of sulfur-containing organic compounds in a concentration
range of 1.0 × 10–5–5.0 × 10–4 M RSD ≤ 5%). The high stability of trimethylsulfonium triiodide and
p-xylylene-bis-(tetrahydrothiophenium) triiodide in chloroform and acetonitrile solutions was found by spec-
trophotometry. A procedure was proposed for the spectrophotometric determination of compounds I and II as ion
associates of sulfur-containing cations with a sulfophthalein dye, Bromocresol Purple (cmin(I) = 1.32 × 10–5 M,
cmin(II) = 7.1 × 10–6 M, RSD = 5%), and by the characteristic absorption of the triiodide anion in acetonitrile
(cmin(I) = 3.18 × 10–6 M, cmin(II) = 2.76 × 10–6 M, RSD ≤ 3%).
DOI: 10.1134/S1061934808070137

Sulfonic ions are used in the organic synthesis as
cationic initiators of polymerization [1] and reagents
for stereospecific alkylation [2].
It is known that, in living organisms, methyltrans-
ferase enzymes use substrates containing chiral sul-
fonic groups as donors of methyl groups [3]. The struc-
ture of enantiomers, asymmetric alkylating agents, was
studied by 1H NMR-spectroscopy using chiral NMR-
shifting reagents [4]. Cyclic sulfonic compounds are a
new type of glucosidase inhibitors [5].
The determination of the structural parameters and
the development of the methods for detecting polyio-
dides of sulfur-containing organic cations, preparations
of active iodine, are of practical interest.
Triiodides of sulfonic cations exhibit a good electric
conductivity of the forwarding type because of the pres-
ence of polyiodide chains [6, 7].
The structural peculiarities of sulfonic cation poly-
iodides in the liquid and solid states are characterized
by the molecular spectroscopy and nuclear magnetic
resonance spectroscopy [8]. The x-ray structure of
Me3SI3 compound in the liquid and solid states is pre-
sented in [9]. In the compounds of the [R3S]Ix type
(R = Me, Et; x = 3–11), the length and symmetry of the
polyiodide chains and the presence of an intermolecu-
lar I–I contact were found out [9–12].
Cyclodextrin-modified capillary-zone electrophore-
sis was proposed as an inexpensive and rapid method
for analyzing a number of tertiary sulfonic and
thiophenic ions [13]. The successive separation of a
series of chiral ion compounds depends on the type of
substituents in the sulfonic ions, the character of the
chiral support, and the presence of tetrabutylammo-
nium bromide as a modifying surface-active cation.
The goal of this work was to assess the ability of tri-
methylsulfonium triiodide (I) and p-xylylenebis(tet-
rahydrothiophenium) triiodide (II) to retain molecular
iodine and to develop a procedure for the quantitative
determination of compounds I and II. The identification
and analysis of the sulfonium and thiophenium cations
were performed by capillary-zone electrophoresis.
Electronic-absorption spectroscopy (UV-spectropho-
tometry) was used to evaluate the stability constants of
triiodides of sulfur-containing cations and as a refer-
ence method.
EXPERIMENTAL
Electronic-absorption spectra of chloroformic
solutions of trimethylsulfonium iodide with various
concentration ratios of organic halide to elemental
iodine were recorded on a Specord UV VIS recording
spectrophotometer using 1.0-cm cells (in the region of
30000–50000 cm–1) and 5.0-cm cells (14000–
30000 cm–1). The starting solution was a 1-mM solu-
tion of trimethylsulfonium iodide and elemental iodine
in chloroform. The concentration of the elemental
iodine was varied in the reaction series from a defi-
ciency to two- to four-fold excess at a constant concen-
tration of the organic iodide of 5.0 × 10–5 M.
The stability constants of p-xylylenebis(tetrahy-
drothiophenium) triiodide were evaluated by the sto-
ichiometric 2-, 4-, 8-, 10-, 16-, and 20-fold dilution of a
2.0 × 10–4 M starting solution. The absorbance was
measured at the wavelength of the absorption of molec-
ular iodine (λ = 510 nm, log ε = 2.95 ± 0.01) using an
SF-46 spectrophotometer and cells l = 1.0 or 5.0 cm.

680
 ELECTROPHORETIC AND SPECTROPHOTOMETRIC DETERMINATION
Reagents. To prepare the reference solutions, accu-
rately weighed portions of I and II were dissolved in
25 mL of a water–acetonitrile mixture in a ratio of 3 : 2
(for capillary electrophoresis) and 2 : 3 (for the deter-
mination as an ion associate, λ = 430 nm) and in aceto-
nitrile (for the determination by the absorption band of
the triiodide ion, λ = 367 nm). Working solutions of
certain concentrations prepared from the initial solu-
tion, were used to construct the calibration curve. A
solution of Bromocresol Purple was prepared by dis-
solving an accurately weighed portion of the reagent
(analytical grade) in water. Organic solvents were
prepurified according to the procedures described in
[14]. We used twice-distilled water in all experiments.
Other reagents were of an analytical grade or better.
Apparatus. Sulfonium cations were determined
using a Kapel’-103R instrument for high-performance
capillary electrophoresis with an unmodified quartz
capillary. In the spectrophotometric determination of
I and II, absorbance was measured on an SF-46 spec-
trophotometer in 1.0-cm cells at the optimal wave-
length. The pH value of the aqueous phase was mea-
sured with a pH-150 pH-millivoltmeter.
Procedures. To record the signals of the electro-
phoretic mobility of sulfonium cations, indirect photo-
metric detection was used at 253.7 nm against a benz-
imidazole buffer solution (6 mM of benzimidazole,
5 mM of tartaric acid, pH 3.51). The analysis was per-
formed at a voltage of 15 kV for 12 min in a quartz cap-
illary with an inner diameter of d = 75 µm, length of
l = 60 cm, and a distance from the sample injection spot
to the detection window of 50 cm (Leff/Ltot = 50/60 cm).
The capillary was successively washed with water, 1 M
HCl, water, 0.5 M NaOH, and water again to wash
NaOH traces, each for 5 min; and then with a buffer
solution for 10 min. Between the experiments, the cap-
illary was washed with the background electrolyte for
3 min without applying voltage. The sample was
injected hydrodynamically at a pressure of 30 mbar for
5 s.
In the extraction-spectrophotometric determination
of sulfur-containing cations, the acidity of the aqueous
phase was maintained with phosphate (pH 6.20) and
borate (pH 8.10) buffer solutions. Chloroform was
selected as an extractant because of its good solvating
ability, low toxicity, and availability. The volume of the
aqueous phase was 10 mL. The chloroform extracts
were dried with anhydrous sodium sulfate and photom-
etered against the extract of the dye solution.
RESULTS AND DISCUSSION
Composition and stability of complexes of trime-
thylsulfonium triiodide and p-xylylenebis(tetrahy-
drothiophenium) triiodide with elemental iodine. To
estimate the degree of complexation, that is, to deter-
mine the number of iodine ions coordinated by the
iodide of sulfur-containing cations and to evaluate the
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63
681
stability of the corresponding polyiodides, the function
of the average iodine number n I2 was used [15]. For
this purpose, the equilibrium in the system organic
iodide–molecular iodine in chloroform was studied by
spectrophotometry.
The equilibrium concentration of iodine [I2] was
calculated from the absorbance at the maximum of the
individual absorption band of the elemental iodine
using Eq. (1)
[ I 2 ] = A max /lε I2 . (1)
For each equilibrium concentration of iodine, the
corresponding value of the function n I2 was found
using Eq. (2):
( c I2 – [ I 2 ] )
n I2 = ------------------------
-, (2)
c KtX
where cKtX and c I2 were the analytical concentrations of
the organic iodide and molecular iodine, respectively.
The stability constant of the monocomplex β (0 <
n I2 < 1) was calculated by the least-squares technique
( log β = 4.63) by Eq. (3) presented in the logarithmic
form:
n I2
- = log [ I 2 ] + log β.
log ------------------ (3)
( 1 – n I2 )
The found value of the effective stability constant of
trimethylsulfonium triiodide is indicative of the stabil-
ity of the symmetric triiodide ion in the chloroform
solution.
The stability of p-xylylenebis(tetrahydrothiophe-
nium) ditriiodide (compound II) was estimated by the
stoichiometric dilution in a chloroform solution con-
taining 5% of acetonitrile. The stability constants of the
monocomplex KtI4 and biscomplex KtI6 were calcu-
lated by the linear least-squares technique using Eq. (4)
(0 < n I2 < 2; β1 = 4.93 × 104; β2 = 3.88 × 108) and by the
nonlinear least-squares technique using Eq. (5) (β1 =
2.34 × 104; β2 = 6.05 × 108):
n I2 ( 2 – n I2 )
- = β 1 + β 2 ------------------
---------------------------- - [ I ], (4)
( 1 – n I2 ) [ I 2 ] ( 1 – n I2 ) 2
β 1 [ I 2 ] + 2β 2 [ I 2 ]
2
n I2 = ----------------------------------------------
-2 . (5)
1 + β1 [ I2 ] + β2 [ I2 ]
The results obtained are in good agreement, which
indicates the reliability of the found values of stability
constants.
Electrophoretic determination of compounds I
and II. The identification and quantitative determina-
tion of trimethylsulfonium triiodide (I) and p-xylyle-
nebis(tetrahydrothiophenium) triiodide (II) were per-
No. 7 2008
682 CHERNOV’YANTS et al.

Table 1. Parameters of the calibration curve Y = k1c + k2 and performance characteristics of the determination of compounds
I and II by capillary electrophoresis

Compound τ, min Parameter k1 k2 ρ cmin × 105, M RSD, %

I 8.60 S, mAUs 8.58 × 103 0.0528 0.999 1.1 1

h, mAU 1.02 × 103 0.0859 0.968 7.8 6

II 9.82 S, mAUs 1.64 × 104 0.155 0.999 1.8 5

h, mAU 1.78 × 103 0.173 0.957 13 6

Table 2. Physicochemical and analytical characteristics of ion associates of compounds I and II with Bromocresol Purple (at
a 40-fold excess of the dye), λ = 430 nm

Compound pH log β n* log ε 430 R, % cmin × 105, M RSD, %

I 6.0–6.4 6.4 ± 0.2 3 4.28 ± 0.05 95.5 1.32 5

II 8.0–8.4 5.7 ± 0.1 3 4.54 ± 0.05 95.6 0.71 5

Note: n is a solvate number.

formed by capillary electrophoresis. The effective elec- Spectrophotometric determination of com-

trophoretic mobility of compounds I and II depends on
the charge, structure, and size of the solvation shell of
the cation component. To obtain well-shaped peaks and
create the optimum conditions for the separation, the
pH of the solution was maintained constant at 3.51. The
migration times of compounds I and II were 8.60 and
9.82 min, respectively, with RSD = 84% for compound
I (c = 6.0 × 10–5 M) and RSD = 94% for compound II
(c = 6.0 × 10–5 M) at n = 6. The complete separation of
the sulfonium cations is characterized by the resolution
Rs = 4.86. The retention times of the halides and triio-
dides of sulfonium cations agreed well.
The determination of organic iodohalides was per-
formed by the linear dependence of the height (h) or
area (S) of the chromatographic peak on the concentra-
tion of the determined compound. Examples of calibra-
tion curves for the electrophoretic determinations are
presented in Table 1. The calibration curves are linear
in the concentration range 1.0 × 10–5–5.0 × 10–4 M.
RSD ≤ 0.05%.
The comparative analysis of the results of the math-
ematical processing of the data on the electrophoretic
separation of sulfur-containing cations shows that the
use of the chromatographic peak area is more advanta-
geous (Table 1). The developed procedure for deter-
mining trimethylsulfonium triiodide and p-xylyle-
nebis(tetrahydrothiophenium) triiodide is characterized
by a sufficient sensitivity and a good precision.
pounds I and II as ion associates with Bromocresol
Purple and by the charge-transfer band of the triio-
dide ion. The formation of ion associates between the
studied sulfonium cations and the anionic sulfophtha-
leine dye, Bromocresol Purple, extracted using chloro-
form was detected by spectrophotometry. For the com-
plete bonding of compounds I and II into ion associates,
a 40-fold excess of the dye and the pH ranges of the
aqueous phase of 6.0–6.4 and 8.0–8.4 for compound I
and II were optimal, respectively. The stability constants
+
of the ion associates of [ Kt I · An–] and [(KtIII)+ · An–]
were evaluated by the Babko dilution method. The
recovery of the ion associates in a single extraction was
no lower than 95%. The results of the physicochemical
study and the determination of the sulfonium cations as
ion associates are presented in Table 2.
A highly sensitive spectrophotometric method was
proposed to control the determination of compounds I
and II, using the charge-transfer band of the triiodide
ion (λmax 295 and 367 nm) in an acetonitrile solution.
The parameters of the calibration curves and their per-
formance characteristics of determining compounds I
and II by the absorption band of the triiodide ion are
presented in Table 3.
The proposed procedure using capillary electro-
phoresis is rapid and simple; it is advantageous for the
separation, identification, and control of the concentra-
tion of sulfonium cations of various natures. At the

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 ELECTROPHORETIC AND SPECTROPHOTOMETRIC DETERMINATION 683

Table 3. Parameters of the calibration curve and performance characteristics of the determination of compounds I and II by
the absorption band of the triiodide ion
A = k1c + k2
Compound λmax, nm cmin × 106, M* RSD
k1 k2 ρ
I 295 4.72 × 104 –0.039 0.9998 3.18 3
367 2.39 × 104 –0.035 6.28 3
II 295 7.49 × 104 –0.030 0.9989 2.67 3
367 3.74 × 104 –0.003 8.02 3
Note: cmin = 5sA.

same time, the spectrophotometric procedures are sim-
pler; they can be characterized by a high sensitivity, and
ensure the determination of the concentration of a com-
pound by both the cation and anion components.
ACKNOWLEDGMENTS
This work was supported by the South Federal Uni-
versity, project no. 05/6-28 of May 28, 2007.
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