Mendeleev Commun., 2021, 31, 306–308
vi
iv
iii
Table 1 Distribution ratios for U , Th , and REE on extraction from
3
1
m HNO3 solution with 0.001 m solutions of compounds 3 and 5 into
,2-dichloroethane.
Oꢀꢉꢂ
Oꢀꢈꢂ
Extractant lgDTh lgDU
lgDNd lgDSm lgDEu
1.87 1.99 1.98
0.0418 0.0418 –0.0218
lgDLn
lgDSm
Nꢀ1ꢂ
Oꢀꢇꢂ
Oꢀꢅꢂ
Pꢀ2ꢂ
3
5
2.21
1.2018
3.10
0.0518
1.39
–0.0218
1.99
0.0418
Oꢀ1ꢂ
Oꢀ2ꢂ
Oꢀꢄꢂ
ꢃꢀ1ꢂ
Oꢀꢆꢂ
Nꢀ2ꢂ
Oꢀ10ꢂ
The extraction properties of bis-phosphine oxide 3 toward
f-block elements were studied by the example of recovery of
Oꢀꢁꢂ Pꢀ1ꢂ
Nꢀꢄꢂ
vi
iv
iii
micro amounts of U , Th , and rare earth elements REE from
m HNO solutions into 1,2-dichloroethane. The efficiency of
3
3
extraction of these elements with solutions of compound 3 was
compared with that for the known extractant, diphenyl(dibutyl-
carbamoylmethyl)phosphine oxide 5 used as a standard in
Figure 1 Molecular structure of complex 4, view as thermal ellipsoids.
1
8
assessment of extraction properties (Table 1).
The complexing properties of new N,O-donor organo-
phosphorus ligand 3 were shown in its reaction with uranyl
nitrate. This reaction in acetonitrile–chloroform solution leads
to [2,3-bis(diphenylphosphoryl)pyridine]uranyl dinitrate 4 in
quantitative yield (see Scheme 1). The slow crystallization of
complex 4 from CH Cl –hexane mixture afforded single crystals
The data of Table 1 show that 2,3-bis(diphenylphosphoryl)-
vi
iv
pyridine 3 exhibits high extraction ability toward U , Th , and
iii
REE and efficiently recovers these elements from nitric acid
solutions. The efficiency of compound 3 considerably (by
hundreds of times) exceeds that of widely used extractant 5.
In summary, we developed a convenient method for preparing
previously unknown N,O-donor bidentate organophosphorus
ligand, 2,3-bis(diphenylphosphoryl)pyridine 3. This ligand can
be used as extractant for recovery of f-block elements from nitric
acid solutions.
2
2
‡
used in X-ray diffraction study (Figure 1).
The obtained crystals contain complex 4 of composition
[
UO (L)(NO ) ] and a solvent molecule in the independent part
2
3 2
of unit cell. The ligand molecule behaves as a bidentate chelate
ligand toward uranyl cation coordinated through both phosphoryl
groups. Two of four phenyl rings are arranged almost in parallel
to each other [the angle between their planes is 9.1(4)°, while the
distance between the centers of the rings is 4.416(6) Å], which
enables one to suppose a C–H∙∙∙π interaction. Nitrate anions
behave as bidentate chelate ligands toward the cation so that
uranium(vi) atom has coordination number eight, while the
The synthesis and study of compounds reported in the paper
was financially supported by the Russian Science Foundation
(project no. 20–13–00329). Spectral and X-ray diffraction
studies were performed using equipment of the Center for
Molecular Structure Studies, A. N. Nesmeyanov Institute of
Organoelement Compounds, Russian Academy of Sciences, and
financially supported by the Ministry of Science and Higher
Education of the Russian Federation.
vi
shape of U O coordination polyhedron is hexagonal bipyramid
8
whose axial positions are occupied by the oxygen atoms
of uranyl cation. The uranyl cation is equal-arm
[r(U=O) = 1.744(6)–1.746(6) Å] and linear [O=U=O angle is
Online Supplementary Materials
1
77.5(3)°]. The equatorial plane is markedly curved, the
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2021.05.009.
deviation of oxygen atoms from the plane is 0.13(1) Å on
average. The complex has insular structure close to that of
previously studied [1,2-bis(diphenylphosphinyl)benzene]uranyl
dinitrate, the maximal deviation of atoms for the two complexes
is not larger than 1.19 Å.
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‡
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29.5 24
3
10 2
6
7
8
monoclinic, space group P2 /n; at 295 K: a = 10.255(4), b = 34.538(15)
1
9
3
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2
F for 6361 observed reflections with I > 2s(I)]. The measurements were
made on a Bruker Quest diffractometer equipped with monochromatized
radiation (l = 0.71073 Å). The structure was solved by direct method,
non-hydrogen atoms were located in difference synthesis of electron
1
1
1
1
5
16
density and refined anisotropically using SHELXTL and OLEX2
2
programs on F . One of phenyl rings and the carbon atom of CH Cl
2
2
solvent molecule are disordered in two positions, non-hydrogen atoms of
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using SADI instructions for C–Cl distance. Hydrogen atoms were added
in ideal positions using the Riding model.
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