Synthesis, IR/Raman, and quantum-chemical structural analysis of new octathiotetraphosphetane ammonium salts

Article abstract of DOI:10.1002/hc.20651

New octathiotetraphosphetane ammonium salts are obtained based on the reaction of white phosphorus (P4) and elemental sulfur with aliphatic mercaptans in the presence of amines (morpholine, methylmorpholine, pyrrolidine, and N,N-dimethylbenzylamine). Both the salts and novel Cu(I) chloride complex with the pyperidinium salt of octathiotetraphosphetane are characterized by IR/Raman spectroscopy in combination with DFT methods. The comparative spectral analysis reveals clear spectral features, characteristic for a P₄S ₈^4- anion, which are present in IR and Raman spectra of all the compounds obtained.

Full text of DOI:10.1002/hc.20651

Heteroatom Chemistry
Volume 22, Number 1, 2011
Synthesis, IR/Raman, and Quantum-Chemical
Structural Analysis of New
Octathiotetraphosphetane Ammonium Salts
Elena K. Badeeva, Elena V. Platova, Elvira S. Batyeva,
Lidiya I. Kursheva, Elena E. Zvereva, Aleksander. E. Vandyukov,
Sergey A. Katsyuba, Valeryi I. Kovalenko, and Oleg G. Sinyashin
A. E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences,
Kazan Scientific Center, 420088, Kazan, Russia
Received 25 May 2010
were obtained by the interaction of white phospho-
ABSTRACT: New octathiotetraphosphetane am-
rus with polysulfides and amines along with other
monium salts are obtained based on the reac-
cyclic thiophosphates; their structures were deter-
tion of white phosphorus (P4) and elemental sul-
mined by the vibrational spectra and X-ray diffrac-
fur with aliphatic mercaptans in the presence of
tion analysis [1–4].
amines (morpholine, methylmorpholine, pyrrolidine,
Using another approach, recently we have
and N,N-dimethylbenzylamine). Both the salts and
reported a new reaction of white phosphorus
novel Cu(I) chloride complex with the pyperidinium
(P4) and elemental sulfur with aliphatic mer-
salt of octathiotetraphosphetane are characterized by
captans in the presence of amines 1a–c, which
IR/Raman spectroscopy in combination with DFT
resulted in formation of ammonium salts of 1,2,3,4-
methods. The comparative spectral analysis reveals
tetramercapto-1,2,3,4-tetrathioxotetraphosphetane
2a–c [5,6]. Their structures determined by the
X-ray diffraction were identified as supramolecular
structures formed by realization of intermolecular
interactions, including N H···S and C H···S ones.
Centrosymmetric thiotetraphosphetane molecules
are connected with four amine molecules by strong
hydrogen bonds. From the point of view of charge
distribution in crystal, the sphere-like associates are
formed [5,6].
In this work, we report about new octathiote-
traphosphetane ammonium salts and some of their
derivatives as well as their spectral (IR/Raman) char-
acteristics to compare their structure with those pre-
viously described [1–6].
4−
clear spectral features, characteristic for a P4S8 an-
ion, which are present in IR and Raman spectra of all
the compounds obtained. 2010 Wiley Periodicals, Inc.
Heteroatom Chem 22:24–30, 2011; View this article online
at wileyonlinelibrary.com. DOI 10.1002/hc.20651
ꢀ
C
INTRODUCTION
Ammonium salts of octathiotetraphosphetanes as
heterocyclic compounds bearing various functional
groups in molecules would be expected to possess
a wide set of useful properties. Earlier, these salts
Correspondence to: L. I. Kursheva; e-mail: kursheva@iopc
.knc.ru.
Contract grant sponsor: Russian Foundation for the Basic
Researches.
RESULTS AND DISCUSSION
Contract grant number: 09-03-00006a.
Contract grant sponsor: Program 6 of the Division of Chemistry
and Material Sciences of Russian Academy of Sciences.
Continuing the research of this reaction, we have
used a range of secondary and tertiary amines, in
particular, morpholine 1d, methylmorpholine 1f,
c
ꢀ
2010 Wiley Periodicals, Inc.
24

Synthesis, IR/Raman, and Quantum-Chemical Structural Analysis of New Octathiotetraphosphetane Ammonium Salts 25
pyrrolidine 1e, and N,N-dimethylbenzylamine 1g
G
F
to synthesize new ammonium salts by the interac-
tion of white phosphorus, sulfur, and butanethiol
or 3-methylbutane-1-thiol. The reaction proceeds
easily at 5–30◦C, according to the previously de-
scribed method for compounds 2a–c [5,6]. Corre-
sponding products 2d–g were light yellow powders
formed with yield 8–15%, being rather stable in solid
as well as in an aqueous solution. Their compo-
sition is confirmed by the elemental analysis data.
E
D
C
P4 + S8 + 4RSH + 4R'NR''2
1a–g
s s
+
+
-
-
-
_
P
P
R'HNR''2
S
S
S R'NHR''2
+ 2(RS)2
+
+
-
_
R'HNR''2
S R'NHR''2
P P
B
A
s
s
2a–g
R' = R'' = Et (a); R' = H, R'' = Et (b); R'= H, R'' = (CH2)5 (c),
R'= H, R'' = (CH2CH2)2O (d); R' = H, R'' = (CH2)4 (e)
R'= Me, R'' = (CH2CH2)2O (f), R'= CH2C6H5, R'' = Me (g)
;
R =
Bu i-Am
In NMR 31P spectra of compounds 2d–g, a singlet
at 121–123 ppm is assigned to this type of salts. Be-
sides, in the reaction mixture after separation of cor-
responding salts, the residue remains (δp 98 ppm),
which is not crystallized and decomposed at vac-
uum distillation. Because of poor quality of crystals
of compounds 2d–g, we were unable to determine
their structure by the X-ray diffraction. Thus, vibra-
tional spectroscopy was applied to their structural
analysis.
700
650
600
550
500
450
400
350
, cm–1
FIGURE 1 IR spectra of 2a (A), 2b (B), 2c (C), 2d (D), 2e
(E), 2f (F), and 2g (G) salt in the selected spectral range 700–
350 cm−1
.
directly from the X-ray data for 2c [6], resulted in a
structure with potential energy ∼1 kcal/mol lower
than the above-mentioned D4h -form. Computed ge-
ometrical parameters of this C1 structure are in a
reasonably good agreement with the corresponding
X-ray values [6] (Table 1).
The experimental Raman and IR spectra of salts
2a–g, registered at 25◦C, are given in Figs. 1–4, re-
spectively. Characteristic bands of the cationic frag-
ments of the compounds, found in the 3600–700
cm−1 spectral range (Figs. 3 and 4), will be de-
scribed later on the discussion of the spectra of
the compounds 2c and 5c. Several bands of strong
and medium intensities, observed in 700–375 cm−1
(IR) and in 700–50 cm−1 (Raman) spectral ranges
The Raman and IR bands of the [P4S8]4− an-
ion calculated for the C1 structure, corresponding
to minimum on potential energy surface, agree very
well with the experimental spectra of 2a (Figs. 5 and
6). The strongest Raman bands at 323, 363, and 177
cm−1 are assigned to symmetric and antisymmetric
stretching of P–P bonds and “breathing” vibration
of the anion, respectively, whereas the strongest IR
bands 660 and 565 cm−1 are assigned to symmetric
and antisymmetric stretching of P–S bonds, respec-
tively. These IR and Raman bands can be used as
reliable spectroscopic markers for the [P4S8]4− an-
ion in the structures of new compounds 2a–g. It
should be noted that our computationally assisted
assignments differ from the earlier empirical inter-
pretation of IR/Raman spectra of related compound
[K4][P4S8]·2H2O [2]. For example, the authors [2]
assigned strong Raman bands at 363 and 177 cm−1
to νPS and to lattice vibrations, respectively, whereas
4−
(Figs. 1 and 2), are assigned to the P4S8 anion [2].
Pronounced differences in frequencies of IR and Ra-
man bands in this spectral range suggest that the rule
of mutual exclusions takes place in our case, similar
to the case of [K4][P4S8]·2H2O [2]. Hence, a center of
symmetry would be expected in the structure of the
anion in the salts 2a–g.
Nevertheless, the quantum-chemically opti-
mized [P4S8]4− structure of the D4h symmetry did not
correspond to minimum on potential energy surface,
as its computed spectrum comprised one imaginary
frequency. Optimization of a starting geometry of
the isolated [P4S8]4− anion of the C1 symmetry, taken
Heteroatom Chemistry DOI 10.1002/hc

26 Badeeva et al.
◦
4−
˚
TABLE 1 Some Experimental and Computed Bond Lengths (A) and Angles ( ) of the [P4S8] Anion
˚
˚
Bond (A)
Angles (A)
˚
˚
Bond (A)
X-ray
Calculated
Angles (A)
X-ray
Calculated
P1–P2
P1–P7
P8–P7
P2-P8
P1–S4
P1–S6
P2–S3
P2–S5
P7–S9
P7–S11
P8–S10
P8–S12
2.288
2.297
2.288
2.297
1.962
1.992
1.978
1.989
1.978
1.992
1.962
1.989
2.360
2.360
2.361
2.362
2.013
2.022
2.012
2.022
2.013
2.022
2.012
2.022
P1–P2–P8
P2–P8–P7
P1–P7–P8
P7–P1–P2
S4–P1–S6
S3–P2–S5
S10-P8-S12
S9–P7–S11
90.03
89.97
90.03
89.077
89.071
89.106
89.97
89.107
118.47
118.75
118.47
118.75
116.448
116.429
116.448
116.429
IR bands at 662 cm−1 and 394 cm−1 were inter-
preted as in-plane deformations of PPP and νPS,
respectively.
In continuation of the study of P,S-containing
ligands ability to the complexation with transition d-
metals, we investigated the behavior of one of salts
of octathiotetraphosphetane, namely pyperidinium
salt, 2c in the reaction with copper(I)chloride. Ow-
ing to the presence of four donor sulfur atoms and
cyclic structure of its molecule, such ligand would
be expected to form a copper(I) complex with cop-
per coordination via the sulfur atoms of the ligand,
as we have earlier established by means of the X-ray
data for the copper(I)complex with triisopropylte-
trathiophosphate [8]. Thus, the reaction of salt 2c
G
F
E
D
C
B
B
A
A
700
600
500
400
300
200
100
, cm–1
ν
3000 1600140012001000 800 600
450 300 150
, cm–1
ν
FIGURE 2 Raman spectra of 2a (A), 2b (B), 2c (C), 2d (D),
2e (E), 2f (F), and 2g (G) salts in the selected spectral range
700–50 cm−1
.
FIGURE 3 Raman spectra of 2c (A) and 5c (B).
Heteroatom Chemistry DOI 10.1002/hc

Synthesis, IR/Raman, and Quantum-Chemical Structural Analysis of New Octathiotetraphosphetane Ammonium Salts 27
B
4
3
2
A
1
700
600
500
400
300
200
100
, cm–1
3000 2500 1600 1400 1200 1000 800
600
400
ν
ν
, cm–1
FIGURE 5 Selected region of the experimental Raman spec-
tra of 2c (2) and 5c (3) in comparison with the calculated
FIGURE 4 IR spectra of 2c (A) and 5c (B).
Raman spectra of the [P4S8]4− anion (1) and [P4S8]4−
(CuCl)4 (4).
-
with Cu(I)Cl in the ratio 1:4 ligand:metal in acetoni-
trile or in methanol at 50–60◦C was conducted. As
a result, the yellow powder was obtained, which de-
composed at temperature higher than 300◦C.
Note that earlier authors of the work on the syn-
thesis of ammonium salt of thiophosphate [1] have
mentioned the formation of the cyclothiophosphates
of some metals, in particular, of the yellow-brown
cyclothiophosphate with Cu(II). However, the prop-
erties of these compounds were not described.
In the NMR 31P spectrum of new compound
5c, a signal of phosphorus at 122 ppm, unchanged
relative to 2c spectrum, is observed. According to
the EPR data, copper in this compound remains its
monovalent state, i.e., Cu(I). The elemental analy-
sis data agree with the composition of the supposed
complex 5c.
To further obtain support for the supposed struc-
ture, IR and Raman spectra of 5c were registered
at 25◦C and compared with the spectra of starting
salt 2c (Figs. 3 and 4). In the 3600–700 cm−1 spec-
tral range, characteristic Raman bands of the pyper-
idinium cations are observed. For example, νCH2
peaks at 2980–2880 cm−1 of 5c are red-shifted by
∼20 cm−1 relative to the spectrum of 2c. Several
new bands, appearing in the 1650–700 cm−1 range
of the spectra of 5c but are absent from the spectra
of 2c, can be assigned to vibrations of the pyperi-
dinium cations coordinated to CuCl. It is remarkable
that several common bands are observed in 700–50
cm−1 range of Raman spectra of salt 2c and com-
plex 5c (Fig. 3), which are unequivocally assigned
above to vibrations of [P4S8]4− anion in the com-
pounds 2a–g. So, we can be sure that [P4S8]4− anion
is present in the structure of both the ligand 2c and
complex 5c.
2c +
CuCl
4
.
.
.
.
.
ClCu .
CuCl
. .S
S
.
.
+
.
+
.
-
S
-
NH2
S
P
P
P
P
N
H2 +
+
In the IR spectrum of the complex 5c (Fig. 4, B),
-
.
.
-
S
S
NH2
N
H2
.
+
νCH2 bands at 2980–2880 cm−1 and νNH2 bands at
.
.
.
.
.
.
CuCl
.
.
S
.
S
ClCu
2463–2367 cm−1 are registered at approximately the
5c
same frequencies as in the spectrum of 2c, though
Heteroatom Chemistry DOI 10.1002/hc

28 Badeeva et al.
4
δCuS
3
2
1
FIGURE 7 Optimized possible structure of the anionic part
of the complex 5c.
700
600
500
400
300
200
100
ν
, cm–1
FIGURE 6 Selected region of the experimental IR spectra of
2c (2) and 5c (3) in comparison with the calculated Raman
spectra of the [P4S8]4− anion (1) and [P4S8]4−-(CuCl)4 (4).
To further clarify the suggested structure of the
complex 5c, quantum-chemical modeling was car-
ried out. A selected model was the [P4S8]4− anion
surrounded by four neutral molecules of CuCl. An
optimized structure, shown in Fig. 7, demonstrates
that the anion retains its structure when each of the
sulfur atoms is coordinated by CuCl. The calculated
Raman and IR spectra of this model agree reason-
ably well with the experimental spectra of 5c (Figs.
5 and 6). Quantum-chemical simulations reproduce
the experimentally observed splitting of νasPS and
νsPS bands, which suggest that CuCl molecules co-
ordinate the ligand 2c via sulfur atoms. According to
the calculations, νCu–Cl band should appear at 250
cm−1 and Cu···S vibrations are predicted to produce
bands in the 200–50 cm−1 spectral region. So, sev-
eral IR/Raman bands in low-frequency region of the
spectra of complex 5c additional in comparison with
the spectrum of “free” ligand 2c may be assigned ei-
ther to νCu–Cl or to the metal-ligand vibrations.
It should be noted that the computed spectra of
another model of (CuCl)4[P4S8]4−, where four CuCl
molecules are situated roughly in the plane of a P4
ring, were in a much worse agreement with the ex-
perimental spectra.
+
νNH2 bands decreased in intensities. In the IR
+
spectrum of the complex 5c, δNH2 bands at 1600
and 1553 cm−1 are more separated than in the spec-
trum of the salt 2c (1600 and 1583 cm−1). The IR
bands of scissoring (δCH2) and wagging (wCH2)
vibrations of the pyperidinium cation (1450–1388
cm−1) and 1128–1056 cm−1 of rocking (ρCH2) vibra-
tions in the spectrum of 5c shift or transform their
contours relative to the spectrum of 2c. The IR ρCH2
band, which is registered at 777 cm−1 in the spec-
trum of 2c, disappears in the spectrum of 5c, but a
new band 430 cm−1 of the pyperidinium cycle skele-
tal deformation is observed instead. As in the case
of the Raman spectra (Fig. 3), common bands of vi-
brations of the [P4S8]4− anion are observed in the
700–350 cm−1 range of IR spectra of the salt 2c and
complex 5c (Fig. 4). Bands at 657 and 567 cm−1 of
νP–S (A, Fig. 4) are split in the spectrum of complex
5c that can point to distortion of the [P4S8]4− anion
in the complex, though the νP–P band at 390 cm−1 re-
mains unchanged. All the above-mentioned spectro-
scopic features demonstrate that both pyperidinium
and [P4S8]4− fragments of the ligand are influenced
by complexation with CuCl.
Thus, a series of new ammonium salts of oc-
tathiotetraphosphetane 2a–g, and a Cu(I)Cl com-
plex 5c with pyperidinium salt 2c are obtained. In
Heteroatom Chemistry DOI 10.1002/hc

Synthesis, IR/Raman, and Quantum-Chemical Structural Analysis of New Octathiotetraphosphetane Ammonium Salts 29
the complex 5c, all sulfur atoms of the octathiote-
Tetra(morpholinium) Salt of 1,2,3,4-tetramerca-
traphosphetane ligand 2c are coordinated by the
copper(I) atoms. The IR/Raman analysis reveals
common spectral characteristics corresponding to
pto-1,2,3,4-tetrathioxotetraphosphetane (2d). Yield
1
10%. mp 178–183◦C. H NMR (D2O), δ: 3.29–3.32
(m, 16H, NCH2), 3.93–3.95 (m, OCH2, 16H); 31P
NMR (D2O), δ: 122.6. Anal. Calcd for C16H40N4O4P4S8
(732): C 26.23; H 5.46; N 7.65; P 16.9; S 34.9. Found:
C 26.75; H 5.41; N 7.34; P 17.31; S 34.46.
4−
the P4S8 anion for all the compounds obtained in
this work, which demonstrates that, regardless of the
character of the compounds formed, their structure
4−
comprises a P4S8 moiety.
Tetra(pyrrolidinium) Salt of 1,2,3,4-tetramerc-
apto-1,2,3,4-tetrathioxotetraphosphetane (2e). Yield
8%. mp 175–179◦C. 31P NMR (D2O), δ: 125. Anal.
Calcd for C16H40N4P4S8 (668): C 28.74; H 5.99; N
8.38; P 18.56; S 38.3. Found: C 28.43; H 6.23; N 8.41;
P 18.72; S 37.82.
EXPERIMENTAL
NMR spectra were measured on a Bruker MSL-400
1
(162.0 MHz, H) and on a Bruker CXP-100 (36.48
MHz, 31P) spectrometers. IR spectra of all com-
pounds were recorded on a FTIR spectrometer “Ten-
sor 27” (Bruker) in the 4000–400 cm−1 middle IR
range at an optical resolution of 4 cm−1. Solid sam-
ples were prepared as KBr pellets. Far-IR spectra
of 2a were recorded on a FTIR spectrometer “IFS-
66v/s” (Bruker) in the 600–100 cm−1 range at an op-
tical resolution of 4 cm−1. Solid sample, mixed with
Nujol, was placed between polyethylene plates. FT
Raman spectra were recorded on a Bruker RAM II
module (using a Ge detector) attached to a Bruker
Vertex 70 FTIR spectrometer in the 4000–10 cm−1
range at an optical resolution of 4 cm−1. The Nd:YAG
laser with a wavelength of 1064 nm (power of 500
mW) was used as a source of excitation. The sam-
ples were placed in a standard cylindrical aluminum
sample pan.
Tetra(N-methylmorpholinium) Salt of 1,2,3,4-
tetramercapto - 1, 2, 3, 4 - tetrathioxotetraphosphetane
(2f). Yield 11%. mp 138–145◦C. 1H NMR (CD3OD),
δ: 2.88 (s, 12H, CH3), 3.2 (m, 16H, NCH2), 3.94 (m,
16H, OCH2); 31P NMR (D2O), δ: 121. Anal. Calcd for
C20H48N4O4P4S8 (788): C 30.46; H 6.09; N 7.1; P 15.7;
S 32.48. Found: C 30.36; H 6.23; N 6.97; P 15.98; S
32.09.
Tetra(N,N-dimethylbenzylammonium) Salt of 1,2,
3,4-tetramercapto-1,2,3,4-tetrathioxotetraphosphet-
ane (2g). Yield 15%. mp 111–115◦C. 1H NMR
(CD3OD), δ: 2.83 (s, 24H, CH3), 4.32 (s, 8H, N-CH2),
7.48–7.54 (m, 20H, HAr); 31P NMR (D2O), δ: 123. Anal.
Calcd for C36H56N4P4S8 (924): C 46.75; H 6.06; N 6.06;
P 13.4; S 27.7. Found: C 47.16; H 6.30; N 5.96; P
13.03; S 27.3.
Solvents and amines were purified by stan-
dard methods. Butanethiol and 3-methylbutane-1-
thiol were obtained from Sigma-Aldrich Rus LLC
(Moscow, Russia). All preparations were carried out
in argon atmosphere.
Tetra(dithiopyperidinium)tetraphosphetane
Copper(I)chloride (5c)
CuCl 0.14 g (1.4 mmol) was added gradually
to
a stirred mixture of 0.25 g (0.3 mmol)
tetraphosphetane 2c in 15–20 mL acetonitrile or
methanol at 28◦ C, and then the reaction mixture was
stirred for 2 h at 50–60◦ C or 35–40◦ C, respectively.
During this time, a white compound was converted
to light-yellow one. After cooling of the reaction mix-
ture to the room temperature, the yellow precipitate
was filtered from the solution and dried to give com-
plex 5c (0.24 g, 61.5%); mp >300◦C (decompos.).
Anal. Calcd. for C20H48N4P4S8Cu4Cl4 (1117): C 21.40;
H 3.97; N 4.99; S 22.87; P 11.0. Found: C 21.12; H
3.25; N 4.77; S 22.93; P 10.2.
Tetraammonium Salts of 1,2,3,4-tetramercapto-
1,2,3,4-tetrathioxotetraphosphetane (2a–g)
General Procedure. Amine (32.7 mmol) was
added dropwise to a stirred mixture of 1 g P4
(32.3 mmol), 2.1 g (64.6 mmol) sulfur, thiol
(32.6 mmol) in CH3CN (8 mL) at 15−30◦C. The mix-
ture was stirred until the reaction was complete
(complete conversion of P4) ≈ 1–2.5 h. The reac-
tion mixture was allowed to stand for 15 h at room
temperature. Then the precipitated crystals of 2a-
g were separated from the solution by decantation,
washed with acetonitrile (3 × 5 mL) and diethyl ether
(2 × 5 mL) and dried. The filtrate was evaporated and
corresponding dialkyldisulfide was distilled from the
residue by means of thin layer distillation Physical,
analytical and spectral data for 2a–c were published
in [5,6].
Computations
All quantum-chemical calculations were carried out
using the Gaussian-03 suite of programs [7]. The
hybrid metageneralized gradient DFT approxima-
tion M05-2X [9,10] was used in combination with
Heteroatom Chemistry DOI 10.1002/hc

30 Badeeva et al.
TABLE 2 Calculated Vibrational Spectra of the [P4S8]4−
Anion
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˚
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G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas,
O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.;
Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.;
Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.,
Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R.
L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.;
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Inc.: Wallingford, CT, 2004.
364
317
287
248
ν P–P
s
δ PS2
δ SPP
δ PS2
241×2
237
Deformation of anion
162×2
160
140
“Breathing” of anion, δ PPP
s
δ
as
PPP
134×2
ω PS2
131
106
104
r PS2
τ PS2
0/ 0
0/ 1
0/ 3
0/ 0
95×2
86
36
Deformation of anion
a
×2, degeneracy.
bν, stretching; δ, bending; ω, wagging; r, rocking; τ, twisting; s, sym-
metrical; as, antisymmetrical.
a standard 6-31G∗ basis set. All stationary points
were characterized as minima by the analysis of
the Hessian matrices. The simulated spectra are ob-
tained by convolution of computed band intensi-
ties with a Lorentzian lineshape function (f.w.h.m.
= 20 cm−1 for the [P4S8]4− model and 10 cm−1 for
the [P4S8]4−(CuCl)4 model). Calculated IR and Ra-
man spectra of [P4S8]4− model are summarized in
Table 2.
[8] Kursheva, L. I.; Ii’in, A. M.; Batyeva, E. S.; Kataeva,
O. N.; Gubaidullin, A. T. Russ J Gen Chem 2001,
71(3), 521.
[9] Zhao, Y.; Schultz, N. E.; Truhlar, D. G. J Chem Phys
2005, 123, 161103.
[10] Zhao, Y.; Schultz, N. E.; Truhlar, D. G. J Chem Theory
Comp 2006, 2, 364–382.
Heteroatom Chemistry DOI 10.1002/hc