Synthesis and conformational analysis of phosphine selenides

Article abstract of DOI:10.1134/S1070363216030154

Methods of preparation of complex phosphine selenide via the original Trofimov–Gusarova reaction are described. The results of the products conformational analysis by means of a set of physical methods (IR spectroscopy, dipole moments, and quantum chemica

Full text of DOI:10.1134/S1070363216030154

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 3, pp. 590–601. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © S.F. Malysheva, N.A. Belogorlova, Ya.A. Vereshchagina, A.Z. Alimova, E.A. Ishmaeva, D.V. Chachkov, 2016, published in Zhurnal
Obshchei Khimii, 2016, Vol. 86, No. 3, pp. 448–460.
To the 100th Anniversary of A.N. Pudovik
Synthesis and Conformational Analysis of Phosphine Selenides
S. F. Malyshevaa, N. A. Belogorlovaa, Ya. A. Vereshchaginab,
A. Z. Alimovab, E. A. Ishmaevab, and D. V. Chachkovc
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
b Kazan Federal University, ul. Kremlevskaya 18, Kazan, Tatarstan, 420008 Russia
e-mail: yavereshchagina@yahoo.com
c Kazan Branch, Joint Supercomputer Center, Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received January 25, 2016
Abstract—Methods of preparation of complex phosphine selenide via the original Trofimov–Gusarova
reaction are described. The results of the products conformational analysis by means of a set of physical
methods (IR spectroscopy, dipole moments, and quantum chemical calculation) are presented.
Keywords: phosphine selenide, the Trofimov–Gusarova reaction, polarity, conformational analysis, quantum
chemical calculation
DOI: 10.1134/S1070363216030154
1. Synthesis of secondary and tertiary phosphine
selenides based on the Trofimov–Gusarova reaction.
Secondary and tertiary phosphine selenides are
attractive as ligands for design of multipurpose metal
complexes [1–4], precursors of physiologically active
compounds [5–9], building blocks of organophos-
phorus compounds [10–15], intermediates of elemental
selenium preparation, and convenient models to study
the physicochemical properties of complex molecules
[19–24]. Conventional methods of phosphine selenides
synthesis utilizing aggressive phosphorus halides and
organometallic compounds are inconvenient, multi-
stage, and environmentally unfriendly. However, these
compounds have been successfully prepared [25–30]
via the Trofimov–Gusarova reaction (direct phos-
phorylation of electrophiles with elemental phosphorus
or the phosphine generated therefrom in the presence
of strong bases) [31–35].
1.1. Synthesis of secondary phosphine selenides
from red phosphorus, styrenes, and elemental
selenium. The synthesis of target secondary phosphine
selenides is based on oxidation of the corresponding
secondary phosphines 1–4 with elemental selenium.
The reaction occurs under mild conditions (ambient
temperature, 0.5–1.5 h, toluene, argon), the yield of
secondary phosphine selenides 5–8 is practically
quantitative [19, 36, 37] (Scheme 1).
The original method of preparation of the starting
secondary phosphines has been elaborated based on
Scheme 1.
R1
R1
R2
R2
R2
Se
Se
PhMe, 20−25oC
P
H
P
H
R2
R1
R1
1−4
5−8
R1 = R2 =H (1, 5); R1 = H, R2 = Me (2, 6); R1 = 4-tBu-C6H4, R2 = H (3, 7); R1 = 4-Cl-C6H4, R2 = H (4, 8).
590

591
SYNTHESIS AND CONFORMATIONAL ANALYSIS OF PHOSPHINE SELENIDES
Scheme 2.
R2
R2
R1
R1
KOH−H2O
[PH3/H2]
Pn
P
H
PhMe, 70−80oC
KOH−DMSO (Н2О),
65−75оС
R1
R2
1−3
R1 = Ph, R2 = H (1, 79%); R1 = Ph, R2 = Me (2, 63%); R1 = 4-ClC6H4, R2 = H (3, 67%).
Scheme 3.
But
KOH−DMSO (H2O)
But
PH3 +
P H
Ar
But
87%
4,
Scheme 4.
Me
Me
Me
KOH−DMSO (Н2О)
Pn +
P
H
200 W, 15 min
2, 54%
nucleophilic addition of phosphine to weakly
electrophilic styrenes in the presence of a superbasic
KОН–DMSO system [36–39]. Phosphine and
hydrogen have been generated in ~1 : 1 ratio from red
phosphorus and potassium hydroxide in a water–
toluene medium [36]. In order to achieve the proper
chemical selectivity of the reaction and to stop it at the
stage of the secondary phosphines formation, the
styrene substrate should be slowly introduced in a
heated KОН–DMSO (H2O) suspension, phosphine
being vigorously passed through the mixture.
tions has been as low as 75%. The process is
chemically selective, and the yield of the secondary
phosphine 4 is 87% (accounting for the conversion of
tert-butylstyrene) [36] (Scheme 3).
Using α-methylstyrene as an example, it has been
demonstrated that secondary phosphine selenide can be
prepared from phosphine, styrene, and elemental
selenium without isolation of the intermediate
secondary phosphine from the reaction mixture [40].
The synthesis of the secondary phosphine 2 via
activation of red phosphorus under combined action of
a strong base and microwave irradiation (200 W,
15 min) has been reported as well. The approach has
allowed for direct phosphorylation of α-methylstyrene
in the Pn–KOH–DMSO(H2O) system affording the
secondary phosphine 2 in 54% yield [37] (Scheme 4).
The following conditions have been suggested for
the synthesis of secondary phosphines 1–3: 60–75°С,
3 h, ratio of alkene : KOH : H2O [1 : 3 : 6.8 for 1 [38],
1 : 5.2 : 2.8 for 2 [37] or 1 : 2.8 : 6.2 for 3 [39] in
DMSO. The yield of the secondary phosphines has
been 79 (1), 63 (2), and 67% (3) (Scheme 2).
The reaction does not occur in the absence of KOH,
the fact evidencing the nucleophilic mechanism of the
process that can be expressed by the Schemes 5, 6.
4-tert-Butylstyrene has been less reactive towards
hydrophosphination than unsubstituted styrene. The
reaction has been performed at 70°С using the ratio
alkene : KOH : H2O (1 : 3 : 1.6) in DMSO. The
conversion of tetr-butylstyrene under the said condi-
The first stage consists in the generation of
phosphide and phosphinite anions from red phos-
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592
MALYSHEVA et al.
with elemental (red or white) phosphorus via the
Scheme 5.
Trofimov–Gusarova reaction [41–43] in a KOH–
DMSO (H2O) system at heating (100°С and 3 h in the
case of red phosphorus, 75°С and 3 h in the case of
white phosphorus; argon). The phosphine yield is 62
(red phosphorus) and 50% (white phosphorus) [41, 42].
The activation with microwave irradiation (300 W) has
decreased the duration of the red phosphorus reaction
with 2-bromopyridine down to 20 min [43] (Scheme 8).
−OH
P−
O
P− +
Pn
phorus under the action of the superbase and micro-
wave irradiation.
Phosphide anions further react with α-methyl-
styrene in a superbasic KОН–DMSO system forming
sequentially the primary and the secondary phosphines
(Scheme 6).
The described reaction occurs likely via initial
splitting of elemental phosphorus by weakly solvated
hydroxide ions yielding phosphorus-centered anions.
Interaction of the latter with 2-bromopyridine via
aromatic nucleophilic substitution mechanism leads to
the formation of tris(2-pyridyl)phosphine (Scheme 9).
1.2. Synthesis of tris(2-pyridyl)phosphine selenide
from 2-bromopyridine, elemental phosphorus, and
elemental selenium. Oxidation of tris(2-pyridyl)phos-
phine 9 with elemental selenium under mild conditions
(ambient temperature, 0.5 h, toluene, argon) has
resulted in quantitative formation of tris(2-pyridyl)phos-
phine selenide 10 (Scheme 7).
This is the first example of formation of the Сsp –P
2
bond directly from elemental phosphorus and hetaryl-
halide.
Hence, the Trofimov–Gusarova reaction is a
convenient approach towards synthesis of organophos-
The starting tertiary phosphine 9 has been synthe-
sized via direct phosphorylation of 2-bromopyridine
Scheme 6.
Me
Me
Me
Me
PH2
Ph
Ph
P−
P
H
KOH−DMSO (Н2О)
KOH−DMSO (Н2О)
Me
2
Scheme 7.
N
N
N
P
Se
P
N
Se
PhMe, 23−25oC, Ar
N
N
9
10
Scheme 8.
N
N
P
N
KOH−DMSO (Н2О)
75oC (P4) or 100oC (Pn), 3 h
+ P4 or Pn
Br
N
9
62% (Pn), 50% (P4)
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593
Table 1. Experimental dipole moments of compounds 5–8
SYNTHESIS AND CONFORMATIONAL ANALYSIS OF PHOSPHINE SELENIDES
phorus compounds (first of all, organic phosphines and
phosphine chalcogenides) based on direct phos-
phorylation of electrophiles (electrophilic alkenes,
acetylenes, and organylhalides) with elemental phos-
phorus (or the generated phosphine) in the presence of
superbases.
Compound
Solvent
Benzene
Dioxane
Benzene
Dioxane
Benzene
Dioxane
Benzene
Dioxane
μexp, D
2.65
3.25
4.16
4.68
3.94
4.63
3.78
3.69
5
6
7
8
2.1. Conformational analysis of secondary aryl-
phosphine selenides. Comprehensive conformational
analysis of complex polyfunctional organic com-
pounds (in particular, organophosphorus compounds
with several axes of internal rotation) has been rarely
reported in the literature; at the best, mutual spatial
arrangement of the molecule fragments has been
discussed. Detailed conformational analysis can be
assessed by the study of the molecules structure in
solution taking advantage of complementary physical
methods; such approach was used in this work.
Csp
3
−Csp
3
bonds, respectively) [20, 21, 44]. Such
mutual orientation of the bonds is typical of the most
of the tetracoordinate phosphorus compounds [49].
Conformers 5b and 5c exhibited similar energy values.
Neither theoretical nor calculated values of dipole
moment of the possible conformers of phosphine
selenide 5 coincided with the experimental data, even
though a series of model compounds with different
surroundings of the phosphorus atom and the reported
polarity were considered to determine the dipole
moment of the P=Se bond (Table 2). It should be noted
that the use of the conformationally uniform rigid
bicyclic selenophosphate [47] as the model compound
was less appropriate, since that molecule contained no
P–C bonds. Even with the lowest dipole moment of the
P=Se bond (2.50 D) [47] used for the calculation, the
theoretical and calculated dipole moments of all the
conformers of compound 5 were lower than the
experimental value. This fact deserves further
investigation involving the extended range of the
phosphorus compounds containing the P=Se bond.
Accounting for the close values of energy of
conformers 5a–5e, they likely contributed almost
equally to the conformational equilibrium.
In view of the scarce data on the structure of
compounds containing P=Se bonds, we performed
conformational analysis of phosphine selenides 5–8
using the method of dipole moments and quantum
chemical calculations [DFT B3PW91/6-31G(d) and
B3PW91/6-311++G(3df,3pd)] [20–23, 44] as well as
IR spectroscopy of compound 6 in different states of
matter [20].
Experimental dipole moments of compounds 5–8
were determined in solutions of benzene and dioxane
(Table 1). Polarity of the selenides 5–8 was typical of
compounds containing tetracoordinate phosphorus
atom, 2.5–5.0 D [45].
In order to base the experimental values of dipole
moments, we calculated all possible conformers of
phosphine selenides 5–8 using the density functional
theory method DFT B3PW91/6-31G(d).
The values of relative energy and dipole moments
(theoretical as well as calculated via the vector-ad-
ditive scheme) of the possible conformers of com-
pound 5 (Fig. 1) are collected in Table 2. The lowest
energy corresponded to the symmetric conformer 5a
X-ray diffraction analysis of phosphine selenide 5
[19] showed that the 5e form with the gauche-
with the Se=P−C
3
sp −Csp
3
dihedral angles of 47° and
orientation of the Р=Se and C
exists in crystal. The crystal packing of the compound
3
sp −Csp
3
bonds (Fig. 2a)
–47° (the g+ and g– orientation of the P=Se and
Scheme 9.
−OH
P−
P
P
P
+
HO
P− +
9
P
−Br−
N
N
Br
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MALYSHEVA et al.
5а
5b
5c
5d
5e
5f
Fig. 1. Possible conformers of compound 5 according to the B3PW91/6-31G(d) simulation.
(b)
(a)
Fig. 2. Geometry of compound 5 molecule (a) in the crystal according to the X-ray diffraction data [19] and (b) crystal packing of
phosphine selenide 5 [19].
(Fig. 2b) showed no π-stacking interactions between
the parallel benzene rings.
compound 6 [20] recorded in different states of the
specimen (crystal, melt, and solution in ССl4 or
CH2Cl2) showed that the number of the bands was the
same for solid and liquid samples (Fig. 3) evidencing
the presence of a single major conformer in all states
or the identity of the spectra of the rotamers in the
400–1600 cm–1 range. It should be noted that the
position of the band assigned to the P=Se bond
vibration (440 cm–1) [19] in IR spectra of compound 6
was the same irrespectively of the state of the
specimen (Fig. 3). That vibration was observed as a
strong band with a maximum at 442 cm–1 in Raman
spectrum of compound 6 (Fig. 4).
Since the experimental and theoretical values of
dipole moments of compound 5 were different, we
calculated the theoretical dipole moments of the preffered
in energy conformer 5a using a variety of quantum
chemical methods and basis sets (Table 3). In general,
the values determined using different non-empirical
methods were fairly close. Hence, we failed to under-
stand the deviation from experimental of the theo-
retical dipole moments of phosphine selenide 5 conformers.
IR spectral data (KBr) for phosphine selenides 5
and 6 have been reported in [19, 40]. An absorption
band of medium intensity at 440 to 600 cm–1 has been
generally assigned to the P=Se bond stretching
vibrations. Comparative analysis of IR spectra of
According to the DFT B3PW91/6-31G(d) quantum
chemical simulation, twelve conformers were possible
for phosphine selenide 6, the 6a-RR, 6a-RS, 6a-SR, and
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SYNTHESIS AND CONFORMATIONAL ANALYSIS OF PHOSPHINE SELENIDES
Table 2. Relative energy and dipole moments (theoretical and calculated using the vector-additive scheme) of compound 5
conformers
m(P=>Se), D (model compound)
ΔE, μtheor
,
3.00 [47]
(EtCl2P=Se)
2.50 [48]
[МеC(CH2O)3P=Se]
Conformer
4.00 [45] (Et3P=Se) 3.73 [46] (Ph3P=Se)
kJ/mol
D
μ
calc, D
5а
5b
5c
5d
5e
5f
0.0
1.0
5.7
7.0
7.5
4.36
4.33
4.42
4.41
4.38
4.64
4.80
4.66
4.74
4.73
4.88
4.38
4.53
4.39
4.47
4.46
4.61
3.67
3.81
3.67
3.75
3.74
3.89
3.20
3.31
3.18
3.26
3.25
3.39
10.3 4.34
6a-SS forms being the most favorable (Table 4 and
Fig. 5) [21, 23, 44]. These were non-symmetrical
than the values for conformer 8a; hence, the conformer
8b was likely the preferred one. The dipole moments
of the conformers calculated via the vector-additive
scheme disagreed with both the theoretical and the
experimental data. Probably, conformers 8a–8c existed
in the conformational equilibrium, since their relative
energies were close.
structures showing the Se=P−C
of 40–60° (gauche-orientation of the P=Se and
sp −Csp bonds); the 6b-RR, 6b–6d-SR conformers
3
sp −Csp dihedral angles
3
C
3
3
were close in energy as well.
Dipole moments of the possible conformers of
compound 6 were calculated using the P=Se bond
polarity values given in Table 4. As expected, the
bicyclic selenophosphate was not a suitable model
compound. The obtained results coincided fairly well
with the experiment (Table 4). Similarly to the case of
compound 5, the equilibrium of the coexisting
conformers close in the energy could not be excluded
for compound 6. That was a reason for the no changes
in IR spectra of compounds 5 and 6 depending on the
state of the specimen (crystal, melt, or solution) [20]:
evidently, the spectral parameters of the conformers in
equilibrium were close.
Similarly, in the case of the phosphine selenide 7
the simulation using different basis sets predicted the
energy preference for different conformers, even
though the simulated dipole moments were close.
Accounting for the slight energy difference between
the conformers (4 kJ/mol as determined in the ex-
tended basis set), the equilibrium of three conformers
of compound 7 in the solution could be expected.
Hence, the dipole moment measurement, IR spec-
troscopy, and quantum chemical calculation showed
Table 3. Dipole moments (μtheor) of the favorable by energy
conformer 5a (ΔE = 0.0 kJ mol–1) determined via various
quantum chemical methods
The simple 6-31G(d) and the extended 6-311++
G(3df,3pd) basis sets were used in the quantum
chemical calculation of the possible conformers of bis-
[(4-tert-butylphenyl)ethyl]phosphine selenide 7 and bis-
[(4-chlorophenyl)ethyl]phosphine selenide 8 [22]. The
resulting most probable conformers are shown in Fig. 6.
Calculation method
PM3
μ
theor, D
5.35
5.04
5.17
4.36
4.36
4.46
4.93
HF/6-31G(d)
In the case of the phosphine selenide 8, the
B3PW91/6-31G(d) results showed that the lowest
energy corresponded to the symmetrical 8a conformer,
however, the simulation in the extended basis set
evidenced the preference for conformer 8b (Table 5).
The dipole moment of the conformer 8b determined in
both sets was in better agreement with the experiment
HF/6-311++G(3df,3pd)
B3PW91/6-31G(d)
B3PW91/6-311++G(3df,3pd)
B3PW91/cc-pVTZ
MP2/6-31G (d)
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MALYSHEVA et al.
D
ν, cm–1
ν, cm–1
Fig. 3. IR spectra of compound 6 in the crystal (1), the melt
(2), and the solution in CH2Cl2 (3).
Fig. 4. Raman spectrum of compound 6 in the crystal.
that compounds 5–8 in the solution were mixtures of
several conformers close in energy; the gauche-orient-
conformational behavior of organic compounds of tri-
and tetracoordinate phosphorus [24]. The earlier
undefined polarities of tris(2-pyridyl)phosphine 9 and
tris(2-pyridyl)phosphine selenide 10 have been
determined, quantum chemical calculation of the
dipole moments of the possible conformers of these
compounds has been performed, and their polarity has
been calculated using the vector-additive scheme [24].
tation of the P=Se and C
coexisting conformations, typical of the rotation
around the Р−Csp bond in the compounds containing
sp3−Csp
3
bonds exists in all the
3
tri- and tetracoordinate phosphorus atom [49].
2.2. Conformational analysis of tris(2-pyridyl)-
phosphine and tris(2-pyridyl)phosphine selenide.
Tris(2-pyridyl)phosphine and its chalcogenides have
been used as convenient models in the study of
Figures 7 and 8 display the values of relative
energy and experimental as well as theoretical dipole
Table 4. Relative energy and dipole moments (theoretical and calculated using the vector-additive scheme) of compound 6
conformers
m(P=>Se), D (model compound)
ΔE,
kJ/mol
μtheor
D
,
4.00 [45] (Et3P=Se) 3.73 [46] (Ph3P=Se)
3.00 [47]
(EtCl2P=Se)
2.50 [48]
[МеC(CH2O)3P=Se]
Conformer
μ
calc, D
6а-RR
6b-RR
6c-RR
6а-SS
6b-SS
6а-RS
6b-RS
6а-SR
6b-SR
6c-SR
6d-SR
6e-SR
0.0
1.9
7.6
0.0
13.0
0.0
8.0
0.0
3.1
5.5
2.2
6.3
4.22
4.14
4.24
4.19
4.29
4.19
4.22
4.13
4.23
4.23
4.31
5.22
4.56
4.63
4.68
4.58
4.77
4.57
4.61
4.73
4.86
4.93
4.16
4.56
4.29
4.36
4.41
4.32
4.50
4.30
4.34
4.46
4.59
4.66
3.90
4.29
3.57
3.63
3.68
3.59
3.78
3.58
3.62
3.74
3.87
3.94
3.19
3.58
3.07
3.13
3.18
3.09
3.28
3.08
3.12
3.25
3.37
3.45
2.70
3.09
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SYNTHESIS AND CONFORMATIONAL ANALYSIS OF PHOSPHINE SELENIDES
6а-RR
6а-RS
6а-SS
6а-SR
Fig. 5. Preferred conformers of compound 6 according to the B3PW91/6-31G(d) calculation.
moments of the possible conformers of compounds 9
and 10. The experimental dipole moment of compound
9 was unexpectedly high (4.16 D); dipole moments of
the trivalent phosphorus compounds typically do not
exceed 3 D [45]. 31P NMR spectrum of phosphine 9
In the case of the unsubstituted phosphine 9
(Fig. 7), two conformations corresponded to the energy
minimum: 9a with the nitrogen atoms of all the three
pyridyl rings being directed towards the P=Y fragment
and 9b with only two pyridyl nitrogen atoms directed
registered under similar conditions (dioxane, δР
=
towards P=Y. The cis-Y–Р–Csp –N dihedral angles
2
–1.44 ppm) was practically identical to that reported in
the literature (–1.98 ppm) [42]; thus, the compound did
not undergo any transformations under the experi-
mental conditions. Further studies confirmed that tris
(2-pyridyl)phosphine was in fact very polar.
were of 50°–60°, corresponding to the gauche,gauche, -
gauche-orientation of the pyridyl rings rotating around
the Р–Csp (cycle) bond. The proportion between the
2
theoretical and experimental dipole moments
evidenced the conformational equilibrium of the 9a
and 9b forms in solution. According to the X-ray
diffraction data [50], weak intermolecular C–H···N
interactions were operative in compound 9, likely
responsible for its high polarity in comparison with the
other trivalent phosphorus compounds [45]. The low
dielectric constant (and, thus, dipole moment) values
According to the calculation data, tris(2-pyridyl)-
phosphine 9 and its selenide 10 have the pyramidal
structure, the pyridyl rings being located in the
propeller shape with respect to the P=Y fragment (Y =
lone-electron pair or Se atom).
Table 5. Relative energy and dipole moments (theoretical and calculated using the vector-additive scheme) of compounds 7
and 8 conformers
B3PW91/6-31G(d)
B3PW91/6-311++G(3df,3pd)
Conformer
μcalc, D
ΔE, kJ/mol
μtheor, D
4.40
ΔE, kJ/mol
0.92
μtheor, D
4.63
7а
7b
7c
8а
8b
8c
0.00
5.65
0.96
0.00
6.42
0.72
4.90
4.91
4.85
5.79
4.28
4.71
4.57
0.00
4.69
4.38
4.14
4.65
5.69
0.35
5.02
3.71
0.00
3.51
4.25
3.51
3.79
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MALYSHEVA et al.
7а
7b
7c
8а
8b
8c
Fig. 6. Possible conformers of compounds 7 and 8 according to the B3PW91/6-311++G(3df,3pd) simulation.
9a
9b
μ
theor = 5.61 D, ΔE = 0.0 kJ/mol
μtheor = 3.82 D, ΔE = 1.8 kJ/mol
Fig. 7. Possible conformers of compound 9 (μexp = 4.16 D, dioxan).
10а
10b
10c
μ
theor = 3.64 D, ΔE = 0.0 kJ/mol
μtheor = 5.85 D, ΔE = 9.1 kJ/mol
μtheor = 8.60 D, ΔE = 26.3 kJ/mol
Fig. 8. Possible conformers of compound 10 (μexp = 4.19 D, dioxane).
are typical of compounds with the intramolecular
hydrogen bonding [51].
rings directed oppositely with respect to the P=Se
group (the trans,trans,trans-orientation of the pyridyl
cycles with respect to the P=Se bond) was the most
favorable conformation (Fig. 8). The 10b conformer
had the trans,trans,cis-orientation of the pyridyl rings
In the case of tris(2-pyridyl)phosphine selenide 10,
the 10a form with the nitrogen atoms of all the pyridyl
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SYNTHESIS AND CONFORMATIONAL ANALYSIS OF PHOSPHINE SELENIDES
with respect to the P=Se bond. The 10c conformer
with the highest relative energy showed the
gauche,gauche,gauche-orientation of the pyridyl rings
with respect to the P=Se bond (Fig. 8). Comparative
analysis of the theoretical and experimental dipole
moments of compound 10 evidenced the predominant
presence of the 10a conformer in the solution, the 10b
conformer being the minor component.
The quantum chemical calculations were performed
as follows. First, the fast search for the possible
conforma-tions of the studied compounds was carried
out applying the DFT B3PW91/6-31G(d) method, and
then the refining calculation was run in the extended 6-
311++G(df,p) basis set. However, in certain cases the
B3PW91/6-311++G(df,p) and the B3PW91/6-31G(d)
calculations evidenced the different conformations
corresponding to the energy minimum. In those cases,
modern wB97XD DFT method was used, including
the exchange functional accounting for the dispersion
intramolecular interactions [54]. When combined with
the extended basis set, the latter method gave better
agreement of the calculated data with the experimental
ones; however, it was more time-consuming.
It should be noted that tris(2-pyridyl)phosphine
oxide and tris(2-pyridyl)phosphine sulfide existed in
the form of the predominant conformer (the pyridyl
rings in gauche- or trans-orientation with respect to the
P=O or P=S bond) in the equilibrium with the second
minor form in the solution [24].
The m(Het→P) group moment of 3.41 D was
determined using the unsubstituted phosphine 9 as the
In the case of the B3PW91 method, the dipole
moment values were practically independent of the
applied basis set, including the set of the Slater
functions. Dipole moments determined using the semi-
empirical PM3 method were somewhat higher than in
the cases of the non-empirical methods. The dipole
moments determined by the different non-empirical
methods were generally close.
model compound. If primary pyridylphosphine (µtheor
2.83 D) or secondary bispyridylphosphine (µtheor
=
=
3.26 D) were used as the model compounds, the
m(Het→P) group moment was of 5.31 and 3.54 D,
respectively. The closeness of the first and the third
mentioned dipole moment values was remarkable.
However, the vector-additive calculation of dipole
moment of the phosphine selenide 10 using those
values did not afford the dipole moment coinciding
with the experimental data. All the calculated dipole
moments were significantly higher (by at least 2 D)
than the experimental value. It should be noted that the
vector-additive dipole moment value was independent
of the direction of the nitrogen atoms of the hetero-
cycles with respect to the P=Y fragment [24].
Quantum chemical calculations were performed
using GAUSSIAN 09 software [55], with full
geometry optimization. The correspondence of the
found stationary points to the energy minimum in all
cases was confirmed by the calculation of the second
derivatives of the energy over the atomic coordinates;
all equilibrium structures corresponding to the
stationary points of the potential energy minimum had
only positive frequencies.
Hence, the method of dipole moments and quantum
chemical calculations revealed that the preferred
conformations of tris(2-pyridyl)phosphine and its
selenide (gauche and trans forms with the propeller-
like orientation of the pyridyl rings with respect to the
P=Y fragment) were in line with the general
conformational behavior of tri- and tetra-coordinate
phosphorus compounds containing alkyl or thioalkyl
substituents.
ACKNOWLEDGMENTS
The calculations were performed at the Kazan
Branch of Joint Supercomputer Center of the Russian
Academy of Sciences.
This work was financially supported by the Russian
Foundation for Basic Research (project no. 16-03-00100a).
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