Electrogeneration of P 2 dianion from P4
–
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 11, November, 2014 2427
4
diameter of 0.32 mm was used. The thickness of phase layer was
9. I. N. Brago, A. P. Tomilov, Elektrokhimiya, 1968, 4, 697
[Sov. Electrochem. (Engl. Transl.), 1968, 4].
0
.25 m. The carrier gas was helium. The mass spectral data
were processed using the Xcalibur program.
Electrochemical reduction of white phosphorus. A solution for
electrolysis was prepared by suspending white phosphorus (70 mg,
10. M. K. Kadirov, Yu. H. Budnikova, K. V. Kholin, M. I. Valiꢀ
tov, S. A. Krasnov, T. V. Gryaznova, O. G. Sinyashin, Russ.
Chem. Bull. (Int. Ed.), 2010, 59, 466 [Izv. Akad. Nauk, Ser.
Khim., 2010, 456].
0
.56 mmol) in a water—ethanol mixture (30 mL) at 50 C.
In some experiments with the Al anode, a small amount of
terephthalaldehyde (0.5 mmol) was added to assess the effect of
organic mediator on the course of the electrochemical process
11. I. M. Osadchenko, A. P. Tomilov, Zh. Prikl. Khim., 1970,
43, 1255 [J. Appl. Chem. USSR (Engl. Transl.), 1970, 43].
12. N. Ya. Shandrinov, A. P. Tomilov, Elektrokhimiya, 1968, 4,
237 [Sov. Electrochem. (Engl. Transl.), 1968, 4].
(
see Table 1). Then, 2 M aqueous HCl (0.5 ml) was added to the
resulted finely divided suspension (opaque solution) and the diꢀ
rect current voltage with a current of 150 mA was applied. During
the electrolysis, the solution became clear. The reaction mixture
was analyzed 10 min after starting the electrolysis by 3 P NMR
spectroscopy and GC/MS. The conditions of electrochemical
processes and the percentages of phosphorus products in the
reaction mixture are given in Table 1. The 31P NMR spectral
characteristics of the phosphorus products obtained correspond
to those published earlier.1
13. V. V. Turygin, A. P. Tomilov, M. Yu. Berezkin, V. A. Fedorꢀ
ov, Inorg. Mater., 2010, 46, 1459.
14. D. G. Yakhvarov, Yu. H. Budnikova, D. I. Tazeev, O. G.
Sinyashin, Russ. Chem. Bull. (Int. Ed.), 2002, 51, 2059
[Izv. Akad. Nauk, Ser. Khim., 2002, 1903].
15. D. Yakhvarov, M. Caporali, L. Gonsalvi, Sh. Latypov,
V. Mirabello, I. Rizvanov, O. Sinyashin, P. Stoppioni,
M. Peruzzini, W. Schipper, Angew. Chem., Int. Ed., 2011,
50, 5370.
1
5
1
6. D. G. Yakhvarov, E. A. Trofimova, I. Kh. Rizvanov, O. S.
Fomina, O. G. Sinyashin, Russ. J. Electrochem. (Engl. Transl.),
2011, 47, 1100 [Elektrokhimiya, 2011, 47, 1180].
7. Pat. RF 85903; Byull. Isobret., 2009, No. 23.
8. R. M. Kagirov, A. V. Voloshin, M. K. Kadirov, I. R.
Nizameev, O. G. Sinyashin, D. G. Yakhvarov, Mendeleev
Commun., 2011, 21, 201.
This work was financially supported by the Russian
Science Foundation (Project No. 14ꢀ13ꢀ01122).
1
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Received September 18, 2014;
in revised form October 28, 2014