Polarity of selected derivatives of diselenophosphinic acid

Article abstract of DOI:10.1134/S1070363217090365

Polarity of diselenophosphinates in benzene solution has been determined by second Debye method. We suggest that these compounds exist as a mixture of several conformers with cis and gauche arrangement of substituents at the phosphorus atom with respect to the P=Se bond.

Full text of DOI:10.1134/S1070363217090365

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 9, pp. 2122–2124. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © Ya.A. Vereshchagina, R.R. Khanafieva, S.F. Malysheva, E.A. Ishmaeva, 2017, published in Zhurnal Obshchei Khimii, 2017,
Vol. 87, No. 9, pp. 1567–1569.
LETTERS
TO THE EDITOR
Dedicated to V. F. Mironov on His 60th Anniversary
Polarity of Selected Derivatives of Diselenophosphinic Acid
Ya. A. Vereshchaginaa*, R. R. Khanafievaa, S. F. Malyshevab, and E. A. Ishmaevaa
a Kazan Federal University, Kremlevskaya ul. 18, Kazan, Tatarstan, 420008 Russia
*e-mail: yavereshchagina@gmail.com
b Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received June 8, 2017
Abstract—Polarity of diselenophosphinates in benzene solution has been determined by second Debye
method. We suggest that these compounds exist as a mixture of several conformers with cis and gauche
arrangement of substituents at the phosphorus atom with respect to the P=Se bond.
Keywords: diselenophosphinate, dipole moments, additive scheme
DOI: 10.1134/S1070363217090365
Derivatives of diselenophosphinic acids are interest-
ing as highly efficient “single-source” precursors of
nanomaterials with unique semiconductive, magneto-
optical, and electrical properties, ligands for the design
of coordination structures, extractants of heavy metals,
additives to lubricating oils, precursors for pharma-
ceuticals, and building blocks in organoelemental
synthesis [1].
Spatial structure of diselenophosphinates 1–6 was
investigated by means of dipole moment and quantum
chemistry methods. The results of experimental and
theoretical conformational analysis of these com-
pounds in solution will be reported separately. Pre-
liminary theoretical calculations data indicated that
each of diselenophosphinates 1–6 existed in solution as
a mixture of several conformers due to the internal
rotation about Р–Csp3, P–Se, or Se–Csp3 bond. Dipole
We determined for the first time the polarity of Se-
methyldiphenyldiselenophosphinate 1, Se-propyldiphenyl-
diselenophosphinate 2, Se-benzyldiphenyldiselenophos-
phinate 3, Se-methyldiphenethyldiselenophosphinate
4, Se-ethyldiphenethyldiselenophosphinate 5, and Se-
benzyldiphenethyldiselenophosphinate 6 in benzene
solution.
Coefficients of the computational equations, orientation
polarizations, and dipole moments (experimental and
calculated via the vector additive schemea) of compounds
1–6
Comp.
no.
R1
Se
α
γ
Рor
μexp, D
μcalc, Da
P
R1
R2
Se
1
2
3
4
5
6
8.165
6.644
7.955
4.827
5.473
6.324
0.393 523.864
0.199 468.550
0.382 645.007
0.333 350.245
0.289 417.886
0.296 556.307
4.94
4.76
5.59
4.17
4.50
5.19
4.79
4.68
4.47
4.06
4.07
4.11
R1 = Ph, R2 = Me (1); R1 = Ph, R2 = Pr (2); R1 = Ph, R2 = Bn
(3); R1 = Ph(CH2)2, R2 = Me (4); R1 = Ph(CH2)2, R2 = Et (5);
R1 = Ph(CH2)2, R2 = Bn (6).
The coefficients of the derived equations, values of
the orientation polarization, and dipole moments (experi-
mental and calculated via vector additive scheme) of
compounds 1–6 in benzene solution are given in the
table.
a μcalc values are given for conformers with zero relative energy.
2122

POLARITY OF SELECTED DERIVATIVES OF DISELENOPHOSPHINIC ACID
2123
moments of the favorable conformers were calculated
using the vector additive scheme (see table).
(0.21 mmol) of n-propyl iodide or 0.27 g (0.21 mmol)
of benzyl chloride was stirred for 30 min at 50–55°С.
The solution was filtered under reduced pressure, and
the excess of the organic halide was removed. Yield
0.60 g (60%) of compound 2 or 0.62 g (72%) of com-
pound 3. The constants for compound 3 coincided with
[7].
From comparison of the experimental and cal-
culated dipole moments of compounds 1–6, we sug-
gested that the forms with zero relative energy took
significant part in the equilibrium of cis and gauche
(with respect to the P=Se bond) conformers.
For determination of experimental values of dipole
moments, we applied the second Debye method based
on the measurement of dielectric constants of dilute
solutions of polar substances in a nonpolar solvent.
The experimental dipole moments were calculated
using Eq. (1) [2]. The orientation polarizations were
calculated using the Guggenheim–Smith equation (2)
[2].
Se-Propyldiphenyldiselenophosphinate (2). IR
(KBr), ν, cm–1: 3052, 2961, 2928, 2869, 3000, 1584,
1478, 1454, 1435, 1377, 1332, 1308, 1279, 1211, 1181,
1159, 1091, 1069, 1027, 998, 744, 689, 618, 553, 506,
1
475, 420. Н NMR (CDCl3), δ, ppm (J, Hz): 0.92 t
3
3
(3H, Me, JНH = 7.2), 1.65 sextet (2H, CH2Ме, JНH
=
7.2), 2.97 d.t (2H, CH2Se, 3JНH = 7.2, 3JНP = 13.1), 7.43
m (6Н, m,p-Ph), 7.92 m (4Н, o-Ph). 13С NMR
(CDCl3), δС, ppm: 14.02 (Me), 23.28 (CH2Ме),
33.47 (CH2Se), 128.15 (p-Ph), 131.28 and 131.37
µ = 0.01283√PorT,
(1)
(2)
3
(o,m-Ph), 132.35 d (ipso-Ph, J = 7.2 Hz). 31Р NMR
3α
3γ
POP = M/d ———– – –———– ,
(CDCl3), δР, ppm: 40.85 + d.d of satellites (1JPSe
=
(ε0 + 2)2 (n02 + 2)2
369.0, 1JP=Se = 764.0 Hz). 77Se NMR (CDCl3), δSe, ppm:
–174 d (1JP=Se = 764.0 Hz), 290.4 d (1JPSe = 369.0 Hz).
Found, %: С 46.39; Н 4.61; Р 8.12; Se 40.96.
С15Н17РSe2. Calculated, %: С 46.65; Н 4.44; Р 8.02;
Se 40.89.
with М, molar mass of the compound; d, density of the
solvent; α and γ, slopes of the εi–wi and ni2–wi linear
plots; εi, ni, and wi, dielectric constant, refractive index,
and mass fraction of the dissolved substance for the ith
solution.
Dielectric constants of solutions of compounds 1–6
were measured in benzene at 25°С using a BI-870
(Brookhaven Instruments Corporation) instrument
with the accuracy of ±0.01. Refractive indexes of the
solutions were measured using an RA-500 (Kyoto Elec-
tronics) refractometer with the accuracy of ±0.0001.
Geometry parameters from theoretical calculations
and the moments of bonds and groups: m(P=>Se) 4.00 D,
calculated from μexp Et3P=Se [3]; m(Csp3→Р) 0.94 D,
calculated from μexp Et2POEt [3]; m(CPh→Р) 1.09 D,
calculated from μexp Ph3P [4]; m(Csp3→Csp ) 0.75 D,
2
ACKNOWLEDGMENTS
calculated from μexp C6H5CН3 [2]; m(Se→P) 1.24 D,
calculated from μexp 4-methyl-2-(methylselanyl)-1,3,2-
dioxaphosphinan-2-oxide [3]; m(Csp3→Se) 0.95 D,
calculated from μexp Et2Se [2]; m(H→Csp3) 0.28 D [5]
were used for the calculation of dipole moments via
the vector additive scheme.
This work was financially supported by the Russian
Foundation for Basic Research (project no. 16-03-
00100а) and the Russian Government Program of
Competitive Growth of Kazan Federal University.
Synthesis of compounds 1 and 4–6 was reported
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