OXIDATIVE HYDROXYLATION OF PHOSPHINE IN AQUEOUS ALCOHOL SOLUTIONS
767
+
4. B. A. Trofimov, N. K. Gusarova, S. I. Verkhoturova,
H O
2
H O
2
I
et al., Russ. J. Gen. Chem. 79, 2453 (2009).
5. N. K. Gusarova, S. L. Verkhoturova, T. L. Kazantseva,
(HO)2HPO
(HO)2IPO
(HO)3PO.
–HI
+
–HI
–H
Derivatives of P(III) with well defined unshared
electron pairs react vigorously with halogens to form
products of nucleophilic addition or substitution:
phosphonium salts and phosphonates. Because РН3
(in contrast to R3P and NH3) has weak nucleophilic
properties, the driving force behind process (5) is to a
great extent the energy of the forming bond. The high
rate of the hydrolysis of iodine derivatives of phosphoꢀ
rus is due to the energy of the resulting P–O (360) and
P=O (612) bonds being higher than that of P–I
(184 kJ/mol) bond.
et al., Mendeleev Commun. 21 (1), 17 (2011).
6. D. V. Sokol’skii and Ya. A. Dorfman, Catalysis by
Ligands in Aqueous Solutions (Nauka, AlmaꢀAta, 1972)
[in Russian].
7. Ya. A. Dorfman, LiquidꢀPhase Catalysis (Nauka,
AlmaꢀAta, 1981) [in Russian].
8. O. N. Temkin, Homogeneous Catalysis with Metal Comꢀ
plexes: Kinetic Aspects and Mechanisms (Akademkniga,
Moscow, 2008; Wiley, 2012).
9. O. N. Temkin, D. S. Bruk, L. S. Zakharova, et al.,
Kinet. Catal. 51, 691 (2010).
10. A. A. Kutyrev and V. V. Moskva, Russ. Chem. Rev. 60
,
72 (1991).
CONCLUSIONS
11. D. V. Moiseev, P. O. Brian, J. R. Brian, et al., Inorg.
A simple С6Н4О2 – I– catalytic system ensuring the
rapid and selective oxidation of РН3 into phosphoric
acid in aqueous alcohol solutions was devised. Due to
the distribution of redox functions between the comꢀ
ponents of the mixed system, a synergetic effect takes
place and the reaction follows a more thermodynamiꢀ
cally advantageous path. Our data confirm the mechꢀ
anism we proposed in [13, 14] for the oxidative alkoxꢀ
ylation of РН3 into phosphorus acid esters in alcohol
solutions of iodine and quinone or redox polymers
based on it. The high rate and selectivity of our cataꢀ
lytic system allows its application in purifying of the
effluent gases of phosphorusꢀproducing plants from
phosphine, and to utilize the latter in the production
of valuable phosphorusꢀcontaining products.
Chim. Acta 363, 3569 (2010).
12. E. E. Ergozhin, T. Hirotsu, B. A. Mukhitdinova, et al.,
in Proceedings of the 40th IUPAC Congress Innovation in
Chemistry, Beijin, China, Aug. 14–19, 2005, p. 516.
13. G. S. Polimbetova, E. E. Ergozhin, B. A. Mukhitdiꢀ
nova, and A. K. Borangazieva, Nauka Studia, No. 4, 48
(2010).
14. B. A. Mukhitdinova, E. E. Ergozhin, G. S. Polimbeꢀ
tova, and A. K. Borangazieva, Euras. Chem.ꢀTechnol.
J. 14, 191 (2012).
15. E. A. Peregud, M. S. Bykhovskaya, and E. V. Gernet,
Express Analysis of Harmful Substances in Air (Khimiya,
Leningrad, 1970) [in Russian].
16. T. S. Zhumadilov, G. S. Polimbetova, A. K. Borangaꢀ
zieva, and B. L. Stanbekova, Izv. NAN RK, Ser. Khim.,
No. 2, 58 (2004).
17. V. I. Zakharov, Extended Abstract of Candidate’s Disꢀ
sertation in Chemistry (AlmaꢀAta, 1992).
18. R. F. Hudson, Structure and Mechanism in Organicꢀ
Phosphorus Chemistry (Academic, London, 1965).
19. J. E. Huheey, Inorganic Chemistry: Principles of Strucꢀ
ture and Reactivity (Harper and Row, New York, 1983).
REFERENCES
1. D. E. C. Corbridge, Phosphorus 2000. Chemistry, Bioꢀ
chemistry, and Technology (Elsevier, Amsterdam, Lauꢀ
sanna, New York, Oxford, Shannon, Singapore, 2000).
2. B. A. Trofimov, S. N. Arbuzova, and N. K. Gusarova,
Russ. Chem. Rev. 68, 215 (1999).
3. B. A. Trofimov, S. I. Verkhoturova, V. L. Mikhailenko,
Translated by M. Makarov
et al., Russ. J. Gen. Chem. 78, 1816 (2008).
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 88
No. 5 2014