ISSN 00405795, Theoretical Foundations of Chemical Engineering, 2010, Vol. 44, No. 4, pp. 467–470. © Pleiades Publishing, Ltd.

, 2010.
Original Russian Text © V.I. Saldin, V.V. Sukhovey, L.N. Ignatieva, A.B. Slobodyuk, V.M. Buznik, Yu.M. Mikhailov, 2009, published in Khimicheskaya Tekhnologiya, 2009,
Vol. 10, No. 4, pp. 193–196.

INORGANIC TECHNOLOGY

Isolation of the DodecahydroclosoDodecaborate Anion

with Chitosan from Aqueous Solutions
V. I. Saldina, V. V. Sukhoveya, L. N. Ignatievaa, A. B. Slobodyuka, V. M. Buznikb, and Yu. M. Mikhailovc
a
Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
b
Institute of Physical Chemistry of Ceramic Materials, Russian Academy of Sciences, Moscow, Russia
cInstitute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia

email: sald@ich.dvo.ru
Received February 14, 2008

Abstract—The possibility of isolating the dodecahydroclosododecaborate anion from aqueous solutions

using chitosan in the form of chitosanium dodecahydroclosododecaborate (C6O4H9NH4)2B12H12 was
studied. The optimum conditions for the precipitation of this scarcely soluble, readily filterable salt and its
decomposition with alkaline reagents were found. The new technique was tested with real aqueous salt solu
2
tions for leaching the products of the hightemperature synthesis of the B12 H 12 anion.
DOI: 10.1134/S0040579510040172

INTRODUCTION of the pyrolysis of NaBH4–NaBF4 [8] and KBF4–

The synthesis and studies of compounds with poly
hedral borohydride anions, in particular, 2
the
dodecahydroclosododecaborate B12 H 12 anion, are
interesting directions in boron chemistry [1, 2] from
the viewpoints of both fundamental knowledge and 2
applications. During the preparation of the B12 H 12
anion, the stage of its isolation from the reaction prod
uct and purification is no less important than2the high
temperature synthesis [3]. Currently, B12 H 12 is most
often precipitated in the form of cesium dodecahydro
closododecaborate Cs2B12H12 followed by its recrystal
lization [4]. However, because of its high solubility, this
salt is inevitably lost with the mother solution, which
2
decreases the yield of B12 H 12 and makes the procedure
more expensive. To avoid these disadvantages, it is pos
sible to use chitosan (C6O4H9NH4)2B12H12. This
deacetylated derivative of chitin is a natural polymer
found in the shell of crab, krill, and insects, as well as in
many fungus species [5]. The structure of chitosan con
tains an NH2 group, due to which this compound
exhibits the properties of a Lewis base and forms an
insoluble salt chitosanium dodecahydroclosodode
caborate (C6O4) (I) [6].
The goal of this study was to develop a procedure for
2–
isolating the B12 H 12 anion from complex aqueous salt
solutions for leaching the products of its hightempera
ture synthesis in the form of I.
EXPERIMENTAL
2–
The procedure for isolating B12 H 12 with chitosan
was tested, as in a previous study [7], on the products
CaH2 mixtures [9].
Chitosan was synthesized at OOO Biopolimery
(Partizansk, Primorskii krai) according to Specs (TU)
9283–174–200472012–03 and had a degree of
deacetylation of 75.3% and a molecular mass of
400000 arb. au.
The precipitates were separated by filtration
through glass filters with porosity no. 4 or centrifuging
on a K 70 D centrifuge at 8000 rpm.
The solubility of I was evaluated by the atomic
adsorption analysis of boron in its saturated solution at
room temperature, which was performed by the stan
dard procedure on an AA780 spectrophotometer.
To evaluate the solubility of chitosanium borate,
tetrafluoroborate, and fluoride, we studied the inter
actions of the salts of these anions with readily soluble
chitosanium acetate [5].
The completeness of the isolation of B12 H 12 with
2–
chitosan in the form of I was controlled by 1H, 11B, and
19F NMR spectroscopy of the solutions using Avance
300 and Bruker WP80SY spectrometers.
The conditions of the decomposition of I were 2–
optimized by the quantitative analysis of the B12 H 12
anion released in the solution in the form of Ag2B12H12
[10] and IR spectroscopic studies of the suspensions of
the powders of the solid residues of decomposed com
pound I in Vaseline oil and KBr pellets in the range of
400–4000 cm–1 using an IFS EQUINOX55S spec
trometer at room temperature.

467
468 SALDIN et al.

Reaction product: K2B12H12, CaF2, KF, KBH4, KBF4, CaH2, B

H2
H2O, HF Leaching, hydrolysis, filtration

Filtrate: K2B12H12, KF, B(OH)3, KBF4, B Precipitate: CaF2, B

C6O4H9NH2 + CH3COOH Deposition of (C6O4H9NH3)2B12H12 filtration

Precipitate: (C6O4H9NH3)2B12H12 B Filtrate: KF, B(OH)3, KBF4, B, CH3COOK

H2O Washing of the precipitate with water

Precipitate: (C6O4H9NH3)2B12H12 B Filtrate: KF, B(OH)3, KBF4, B, CH3COOK

NH4OH
Preparation of (NH4)2B12H12 Utilization of fluorine CaO, H2O
filtration filtration

Precipitate C6O4H9NH2 Filtrate (NH4)2B12H12 Precipitate CaF2

Evaporation, drying Evaporation, drying

Filtrate (NH4)2B12H12 KOH

(end product)
For the preparation of the salts of B12H122–anion

2–
Fig. 1. Diagram of the isolation of the B12 H 12 anion using chitosan from the product of the pyrolysis of a KBF4–CaH2 mixture.

RESULTS AND DISCUSSION
The composition of the reaction products, from
2–
which B12 H 12 was to be isolated, depends on the par
ticular methods for the preparation of the anion,
described here by the following equations:
36NaBH 4 + 10NaBF 4
(1)
= 3Na 2 B 12 H 12 + 40NaF + 10B + 54H 2 ,
46KBF 4 + 72CaH 2
(2)
= 3K 2 B 12 H 12 + 72CaF 2 + 40KF + 10B + 54H 2 .
After the dissolution in water in a ratio of 3 : 1 (HF
should be added for decomposing MBH4) and the sub
sequent separation of the precipitates of the scarcely
soluble products (Fig. 1), the filtrate contained the
desired Na2B12H12 and K2B12H12 with admixtures of
NaF and KF (byproducts), NaBF4 and KBF4 (resid
ual starting compounds), and B(OH)3 (the product of
the hydrolysis of the residual NaBH4 and KBH4) [7].
If chitosan is regarded as a precipitating agent for
2–
B12 H 12 , it should satisfy four conditions. First, it
2–
should form a not readily soluble salt with B12 H 12 .
Second, the resulting salt should be easily separable
2–
from the solution. Third, any other salt of the B12 H 12
anion should be readily obtained from it. Fourth, chi
2–
tosan should be selective with respect to B12 H 12 .
The first condition was well observed for I. As
shown by studies of its solution saturated at room tem
perature, boron was detected at the level of the sensi
tivity of the atomic adsorption method, which was not
more than 1 µg/ml. It is easy to calculate that the
product of the solubility of I is not more than 9.1 × 10–
16
. This indicates that I is comparable in this character
istics to Ag2B12H12, whose solubility product is 3.9 ×
10–16 and which is used as a weight form in the quanti
2–
tative analysis of the B12 H 12 anion [10]. Therefore,
the loss of the polyhedral borohydride anion was abso
lutely excluded for I in contrast to Cs2B12H12, whose
solubility is 2.7 g/100 g of water at 25°C [4].
According to our experiments, the second condi
tion was also satisfied for I. The use of a 1.0–1.5%
solution of chitosanium acetate and a 2–10% solution
2–
of B12 H 12 was optimum for the formation of a well
filterable precipitate of I. Filtrates with this concentra
2–
tion of B12 H 12 were obtained after the separation of
the precipitates from the leaching solutions [7,
2–
Table 2]. For the complete precipitation of B12 H 12 ,

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

 ISOLATION OF THE DODECAHYDROclosoDODECABORATE ANION 469

chitosanium acetate should be taken in a small excess 100

relative to the reaction stoichiometry,
2C 6 O 4 H 9 NH 3 CH 3 COO + ( Na, K ) 2 B 12 H 12

Degree of deposition of I, %
(3) 80
= ( C 6 O 4 H 9 NH 3 ) 2 B 12 H 12↓ + 2CH 3 COO ( Na, K ).
At lower concentrations of the reagents, I was sep 60
arated in the form of a finely disperse precipitate,
which at first passed through the porous glass filter (4)
and then clogged it, while filtering stopped completely. 40
1
The centrifuging of these milky white solutions gave 2
precipitates containing more than 50 wt % of the 20 3
mother solution, and the additional washing of the 4
precipitate was thus needed. At higher concentrations
of the reagents, I was isolated in the form of flaky or
2– 0 1 2 3 4 τ, h
skinlike films, from which the B12 H 12 anion was
much more difficult to separate in the solution. Fig. 2. Dependence of the extent of decomposition of I on
For this purpose, one can use the alkaline treat the nature of the alkaline reagent, molar ratio of the
reagents, temperature, and time for (1) NH4OH, 1 : 1,
ment of I. As is known for other chitosan salts [5], this 20°C; (2) NaOH 1 : 1, 20°C; (3) NH4OH, 2 : 1, 40°C; and
leads to their decomposition that forms freshly precip (4) NH4OH, 2 : 1, 80°C (rate of stirring of 60 rpm).
itated chitosan. If alkaline (Li, Na, K) and ammonium
hydroxides are used, the decomposition of I can be most suitable form of the end product containing the
described by the equation 2–
B12 H 12 anion.
( C 6 O 4 H 9 NH 3 ) 2 B 12 H 12↓ + 2MOH
(4) Finally, as shown by studies of the exchange reac
= C 6 O 4 H 9 NH 2↓ + M 2 B 12 H 12 + 2H 2 O. tions between the 1.5% aqueous solution of chitosa
After freshly precipitated chitosan is separated, the nium acetate and NaF, KF, NaBF4, KBF4, and H3BO3
2– solutions, which are impurities for Na2B12H12 and
B12 H 12 anion passes to wellsoluble ammonium and K2B12H12, none of these reactions formed precipitates.
alkaline salts. This is indicative of the rather high solubility of chito
Note that the decomposition of I is a heterophase san salts with fluoride, tetrafluoroborate, and borate
process. The rate and extent of decomposition are lim anions. Therefore, it is considered that chitosan is a
ited by the rate of the diffusion of hydroxyl anions to 2–
selective precipitator of B12 H 12 from solutions con
the inner layers of the particles of the scarcely soluble taining this set of anions.
compound I. The insoluble chitosan formed in the
reaction accumulates on the surface of the particles To summarize, chitosan satisfies all of the above
2–
requirements for its use as a precipitation form of the
and also hinders the exit of B12 H 12 in the reverse 2–
B12 H 12 anion. Importantly, freshly precipitated chito
direction from the inner layers to the solution. As
would be expected, the process is markedly acceler
ated when it is performed at elevated temperatures and
increased reaction times with vigorous stirring BRUKER 2482
(Fig. 2). The reaction rate also increases in the pres *
ence of an excess of the alkaline agent. For this pur *
pose, ammonium hydroxide (NH4OH) is the most 3 *
2473
suitable. This is a widely accessible and relatively inex
Absorption

pensive, strongly alkaline reagent. The use of NH4OH *

does not lead to any problems at the stage of purifica
tion of the desired M2B12H12 product from the excess
alkaline reagent. After the evaporation to dryness that 2 *
forms solid (NH4)2B12H12 (Fig. 1), the excessive
NH4OH completely passes to the gas phase. The com *
plete decomposition of I under the action of excess 1
NH4OH (Fig. 2, curve 4) to the starting chitosan is
indicated by the absence of the 2480cm–1 band corre 4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
sponding to the B–H stretching vibrations in the Wave number, cm–1
2–
B12 H 12 anion in the IR spectrum of the solid residue
(Fig. 3) [11]. In addition, as noted in [7], (NH4)2 is the Fig. 3. IR spectra of (1) Cs2B12H12, (2) chitosan, and (3) I.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

470 SALDIN et al.
san can be repeatedly used in a closed cycle (Fig. 1),
which affects the effectiveness of the method for the
2–
isolation and purification of the B12 H 12 anion. More
over, the suggested procedure provides for the com
plete utilization of fluorine into CaF2 as a byproduct,
which is a raw material for the production of fluorides
and fluorine, as well as KOH, a widely used chemical
reagent.
CONCLUSIONS
Based on the experimental data, we have consid
2–
ered the possibility of isolating the B12 H 12 anion from
complex aqueous salt solutions for leaching the prod
ucts of its hightemperature synthesis and purifying
with chitosan without using cesium salts. The desired
2–
B12 H 12 anion obtained by this procedure is much less
expensive. This method can be recommended for iso
lating this valuable anion from the industrial solutions
2–
obtained during the synthesis and use of the B12 H 12
anion.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (project no. 0703
12057ofi).
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