An unusually stable pyridine-2-selenenyl chloride: structure and reactivity

Article abstract of DOI:10.1007/s11224-016-0845-3

According to an X-ray diffraction study, pyridine-2-selenenyl chloride (1) characterized by unusually high stability both in solutions and in the solid state adopts a dimeric structure formed by two secondary intermolecular Se···N interactions. However, it slowly transforms into zwitterionic T-shaped pyridinium-2-selenenyl dichloride (2) in a dichloromethane solution. Conformational features, electronic structures, and reactivities of 1 and 2 are discussed on the basis of experimental and theoretical (quantum chemical calculations) data.

Full text of DOI:10.1007/s11224-016-0845-3

Struct Chem
DOI 10.1007/s11224-016-0845-3
ORIGINAL RESEARCH
An unusually stable pyridine-2-selenenyl chloride: structure
and reactivity
Victor N. Khrustalev1,2
Zhanna V. Matsulevich3 Rinat R. Aysin2
•
•
•
Julia M. Lukiyanova3 Georgy K. Fukin4 Yan V. Zubavichus5 Rizvan K. Askerov6
Abel M. Maharramov6 Alexander V. Borisov3
•
•
•
•
•
Received: 15 July 2016 / Accepted: 31 August 2016
Ó Springer Science+Business Media New York 2016
Abstract According to an X-ray diffraction study, pyr-
idine-2-selenenyl chloride (1) characterized by unusually
high stability both in solutions and in the solid state adopts
a dimeric structure formed by two secondary intermolec-
ular SeÁÁÁN interactions. However, it slowly transforms into
zwitterionic T-shaped pyridinium-2-selenenyl dichloride
(2) in a dichloromethane solution. Conformational features,
electronic structures, and reactivities of 1 and 2 are dis-
cussed on the basis of experimental and theoretical
(quantum chemical calculations) data.
Introduction
The stabilization of arenechalcogenyl halides is typically
achieved via the intermolecular coordination of the
chalcogen atom to electron-donor functional groups (often
nitrogen- or oxygen-containing ones) in the ortho-position
with respect to the chalcogenyl halide group [1–15].
Recently, we have synthesized the very first representative
of hetarenetellurenyl halides bearing pyridine as a hetaryl
fragment—2-pyridinetellurenyl chloride (1a), and the
dimeric structure of this compound was established [16].
With this respect, it was important to further elucidate
factors governing the prominent stability of its close ana-
logue, 2-pyridineselenyl chloride (1b) actually synthesized
more than 30 years ago [17]. As we have found recently,
1a slowly spontaneously converts into the T-shaped adduct
2a in a dichloromethane solution [18]. Furthermore, we
have shown that complexes 1a and 2a can act as efficient
reagents in the polar cycloaddition to multiple bonds
[18–20].
Keywords Pyridine-2-selenenyl chloride Á T-shaped
adduct Á Conformational analysis Á Molecular structure Á
DFT calculation Á Crystal structure
This paper is dedicated to Prof. Vladimir Shevchenko (Institute of
Silicate Chemistry of Russian Academy of Sciences, Saint-
Petersburg, Russia) on the occasion of his 75th anniversary.
& Victor N. Khrustalev
vnkhrustalev@gmail.com
In the present paper, we establish the molecular and
crystal structures of 2-pyridineselenyl chloride and study
reasons for its high stability in relation to capabilities of its
further transformations and modifications.
1
Peoples’ Friendship University of Russia, Miklukho-Maklay
St., 6, Moscow, Russian Federation 117198
2
A. N. Nesmeyanov Institute of Organoelement Compounds
of RAS, Vavilov St., 28, Moscow, Russian Federation
119991
Experimental
3
R. E. Alekseev Nizhny Novgorod State Technical University,
Minin St., 24, Nizhny Novgorod, Russian Federation 603950
Synthesis of 1b and 2b
4
G. A. Razuvaev Institute of Metalloorganic Chemistry of
RAS, Tropinin St., 49, Nizhny Novgorod, Russian Federation
603137
Starting reagents were purchased from Sigma-Aldrich and
used without further purification. Melting points were
measured on a ‘‘Boetius’’ bench. Elemental analysis was
accomplished with an automated PerkinElmer 2400 CHN
microanalyzer.
5
National Research Center ‘‘Kurchatov Institute’’, Acad.
Kurchatov Sq., 1, Moscow, Russian Federation 123182
6
Baku State University, Z. Khalilov St., 23, 1148 Baku,
Azerbaijan
123

Struct Chem
1b Pyridine-2-selenenyl chloride was obtained by the
method described previously [17], but using dichlor-
omethane as a solvent instead of ethyl acetate. Mp
136–138 °C ([17]: 118–119 °C). C5H4NClSe (192.51):
calcd. C 31.20, H 2.09, N 7.28; found C 31.15, H 2.21, N
7.37.
Results and discussion
Molecular and crystal structures
Molecules of 1b occur in the crystal structure as dimers
formed by the Se/N interactions (Fig. 1), exactly as in the
case of tellurium analogue 1a.
2b Pyridine-2-selenenyl chloride (0.05 g, 0.26 mmol)
was dissolved in dichloromethane (100 mL) at room tem-
perature. After 168 h, the solvent was evaporated in vacuo.
The precipitate contained 0.059 g (100 %) of a yellow
powder T-shaped 1H-pyridine-2-selenenyl dichloride (2b).
Mp 145–146 °C. C5H5NCl2Se (228.97): calcd. C 26.23, H
2.20, N 6.12; found C 26.17, H 2.34, N 6.22. Single
crystals of 2b suitable for an X-ray diffraction analysis
were prepared by a slow evaporation of a solution in
dimethylformamide/diethyl ether (9:1) solvent mixture at
room temperature.
The molecule of 1b adopts a butterfly conformation with
the fold angle on the SeÁÁÁSe line of 70.07(7)°. The Cl1–
Se1/N2 and Cl2–Se2/N1 fragments are almost linear
(177.93(7) and 175.30(7)°, respectively). The C2–Se1 and
˚
C7–Se2 distances of 1.926(3) and 1.918(3) A are equal to
each other and correspond well to single bonds. The Se1/
˚
N2 and Se2/N1 distances of 2.141(3) and 2.189(3) A fall
in the range of those within the related T-shaped sele-
˚
nium(II) complexes (1.931(4)–2.204(5) A [29]).
It is interesting to point out that the Cl1 atom forms
secondary interactions with the both selenium atoms
[Se1ÁÁÁCl1 (-x, 1 - y, 2 - z) 3.6603(9) and Se2ÁÁÁCl1
X-ray crystallography
˚
(1 - x, -y, 2 - z) 3.7500(8) A], whereas the Cl2 atom
remains free of any non-valent contacts. Due to the inter-
molecular SeÁÁÁCl interactions, the selenium atoms have a
distorted square-planar coordination (Fig. 2). Moreover,
just these additional interactions result in the elongation of
˚
the Se1–Cl1 bond [2.4041(3) A] as compared to the Se2–
˚
Cl2 one [2.3657(3) A].
Data were collected using Bruker APEX CCD (for 1b) and
APEX-II CCD (for 2b) diffractometers [k(MoKa)-radia-
tion, graphite monochromator, x and u scanning modes]
and corrected for absorption using the SADABS program
[21]. For details, see Table 1. The crystal structures were
determined by the direct methods and refined by a full-
matrix least squares technique on F2 with anisotropic dis-
placement parameters for non-hydrogen atoms. The crystal
of 2b contained a solvate dimethylformamide (DMFA)
molecule. The pyridinium NH hydrogen atom in 2b was
objectively localized in the difference-Fourier map and
refined isotropically with fixed isotropic displacement
parameters [Uiso(H) = 1.2Ueq(N)]. The other hydrogen
atoms in both complexes were placed in calculated posi-
tions and refined within the riding model with fixed iso-
tropic displacement parameters [Uiso(H) = 1.5Ueq(C) for
the CH3 groups and 1.2Ueq(C) for other groups]. All cal-
culations were carried out using the SHELXTL program
[22]. Crystallographic data for 1b and 2bÁDMFA have been
deposited with the Cambridge Crystallographic Data
Center.
In the crystal, molecules of 1b form the ribbons parallel
to (110) via the intermolecular secondary SeÁÁÁCl interac-
tions described above (Fig. 2).
Earlier based on NMR data, we suggested that strong
proton acceptors (DMSO, DMFA, etc.) can cleave the
stabilizing intramolecular N–HÁÁÁCl H-bond in zwitterionic
T-shaped hetarylselenenyl chlorides giving rise to a ‘‘pro-
peller’’-type molecular motion in such solvents (Scheme 1)
[30]. Making such a suggestion, we kept in mind that an
H-bond is directional, which makes it similar to a normal
polar covalent bond, only a weak one [31]. Our arguments
were well stipulated, but still the formation of a bifurcate
H-bond with the proton bonding simultaneously inter-
molecularly to a solvent molecule and intramolecularly to a
chlorine atom of the –SeCl2 moiety cannot be totally ruled
out.
Remarkably, upon recrystallization, we have isolated the
H-bonded complex of 2b with a molecule of DMFA in the
solid state and studied its structure by single-crystal X-ray
crystallography. It appeared that the DFMA molecule
being a stronger proton acceptor actually cleaves the
intramolecular N–HÁÁÁCl H-bond avoiding the formation of
a bifurcate-type H-bond (Fig. 3). The parameters of the
intermolecular N–HÁÁÁO hydrogen bond are following: N–
Computational details
All theoretical calculations of geometry and normal coor-
dinate analysis (NCA) for 1b and 2b were performed using
the Gaussian 03 [23] program at the DFT level of theory
using the PBE0 [24] and M06-2X [25] functionals;
6-311??G(d,p) [26, 27] valence basis sets were utilized
for all atoms. The R. Bader’s QTAIM analysis of electron
density was performed in the AIMAll program [28] at the
M06-2X/6-311??G(d,p) level of theory.
˚
˚
˚
H 0.80(2) A, HÁÁÁO 1.90(2) A, NÁÁÁO 2.6563(19) A, \N–
HÁÁÁO 159(2)°. Furthermore, the 2-pyridineselenyl chloride
123

Struct Chem
Table 1 Crystal data and
experimental parameters for 1b
and 2b
Compounds
1b
2bÁDMFA
Molecular formula
Formula weight
Crystal system
Space group
C10H8Cl2N2Se2
385.00
C8H12Cl2N2OSe
302.06
Triclinic
P¯ı
Monoclinic
P21/c
˚
a (A)
7.4651 (4)
8.6227 (4)
10.2077 (5)
77.229 (1)
83.049 (1)
72.354 (1)
609.62 (5)
2
12.0570 (4)
11.5026 (4)
8.5326 (3)
90
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
94.585 (1)
90
3
˚
V (A )
1179.57 (7)
4
Z
d (g cm-3
)
2.097
1.701
Absorption coefficient (mm-1
)
6.475
3.607
F(000)
368
600
Crystal size (mm)
0.20 9 0.15 9 0.10
2.53–26.99
4067
0.15 9 0.15 9 0.10
2.45–30.99
16,421
h range for data collection (°)
Reflections collected
Independent reflections
Reflections with I [ 2r(I)
Number of parameters
Goodness-of-fit on F2
R1 [I [ 2r(I)]
2622
3764
2390
3224
145
132
1.050
1.015
0.0333
0.0259
wR2 [I [ 2r(I)]
0.0866
0.0668
T
min, Tmax
0.336, 0.565
0.852 and -0.333
922,925
0.606, 0.707
0.749 and -0.264
1,055,674
-3
)
˚
Largest diff. peak and hole (e A
CCDC no.a
a
Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (http://www.ccdc.cam.ac.uk)
molecule adopts the twist conformation with a twisting
angle between the pyridyl and –SeCl2 planes of 48.49(5)°
rather than the planar conformation typical of other anal-
ogous zwitterionic T-shaped selenium complexes stabilized
by a strong intramolecular N–HÁÁÁCl H-bond (Fig. 4) [30].
This solidly and directly supports the mechanism actuating
the molecular dynamics of T-shaped hetarylselenyl chlo-
rides in proton-acceptor solvents, and thus zwitterionic
structure of T-shaped chalcogenide complexes with a
common formula [H(hetAr)]ChHal2, where hetAr is a
hetaryl substituent [32].
˚
The C–Se distance of 1.9195(15) A in 2b is represen-
tative of single bonds {the lengths of C=Se bonds in
1-methylbenzoimidazoleselone, benzothiazoleselone, and
˚
N-methylbenzothiazole-2-selone are 1.838(2) A [33],
˚
˚
1.8236(11) A [34], and 1.817(7) A [35], respectively}.
The Cl2 atom in 2b is involved in the intermolecular
secondary SeÁÁÁCl interaction [Se1ÁÁÁCl2 (x, ‘ - y,
Fig. 1 Molecular structure of 1b
123

Struct Chem
Fig. 2 Crystal packing of 1b demonstrating the ribbons parallel to (110). The dashed lines are indicative of the intermolecular secondary SeÁÁÁCl
interactions
Cl
Se
Cl
S
N
.
.
+
.
.
.
.
H
.
.
.
.
.
.
DMSO
Scheme 1 Dynamic propeller-like process in solution of zwitterionic
T-shaped hetarylselenenyl chlorides
˚
-‘ ? z) 3.3786(4) A]. Thus, the selenium atom in 2b
adopts a distorted square-planar coordination (Fig. 5). Due
to the intermolecular SeÁÁÁCl interaction, molecules of 2b
form the zigzag-like chains along the crystallographic
c axis (Fig. 5). As a result of the intermolecular interaction,
the SeCl2 moiety in 2b has asymmetric geometry with the
˚
Se–Cl2 bond [2.4566(4) A] being longer than the Se–Cl1
˚
bond [2.3929(4) A]. The mean value of the two Se–Cl
˚
bond lengths in 2b [2.4248(4) A] is significantly larger
than those in the two-coordinate selenenyl(II) chlorides
˚
˚
˚
{[2.177(1) and 2.184(1) A [2], 2.164(2) A [6], 2.188(3) A]
[36]}.
Fig. 3 Molecular structure of 2bÁDMFA. The intermolecular N–
HÁÁÁO hydrogen bond is drawn by dashed line
Calculation results
hypothetical monomeric (1m) forms. The results obtained
using two different functionals PBE0 and M06-2X are
virtually identical and self-consistently indicate that the
dimer formation is energetically favorable both in the solid
In order to gain a deeper insight into the stabilization
mechanism of 2-pyridineselenyl chloride, we performed
quantum chemical calculations for its real dimeric (1d) and
123

Struct Chem
Fig. 4 Planar conformation of benzothiazolium-2-selenenyl dichloride stabilized by the intramolecular N–HÁÁÁCl hydrogen bond. The
intramolecular N–HÁÁÁCl hydrogen bond is drawn by dashed line
Fig. 5 Crystal structure of 2b demonstrating the zigzag-like chains along the c axis. The dashed lines are indicative of the intermolecular N–
HÁÁÁO hydrogen bonds and secondary SeÁÁÁCl interactions
Table 2 Results of calculation
for the 2-pyridylselenenyl
chloride dimerization
1
Functional
DEtot, a.u.
DHo, a.u.
DGo, a.u.
Monomer (1m)
PBE0
-3108.662365
-3109.307793
-6217.353919
-6218.645118
-18.32
-3108.653912
-3109.299351
-6217.336839
-6218.628021
-18.21
-3108.697340
-3109.343286
-6217.400251
-6218.691764
-3.50
M06-2X
PBE0
Dimer (1d)
M06-2X
PBE0
DE, kcal/mola
M06-2X
-18.53
-18.40
-3.26
a
ZPVE correction is applied
state and in solutions (Tables 2, 3). It is also of note that the
hypothetical planar dimer is not realized as a local mini-
mum of the potential energy surface: It undergoes a nearly
barrierless transformation into the butterfly conformation
with a folding angle of *100°.
is slightly lower than for similar benzimidazole and ben-
zothiazole derivatives (11–13 kcal/mol [30]).
We applied QTAIM analysis in order to identify dimer-
forming attractive interactions. The respective results are
summarized in Fig. 7 and Table 4. As it can be clearly seen
in molecular graph 1d (see Fig. 7), the dimer is formed by
two strong Se/N bonds with energy of 10.8 kcal/mol each
The barrier to rotation of the –SeCl2 linear fragment
around the C–Se bond in 2b is 9.0 kcal/mol (Fig. 6), which
123

Struct Chem
Table 3 Geometrical (X-ray
and calculated) parameters for
1m, 1d, and 2b
˚
Se–C, A
˚
˚
˚
Molecule Method
Se–Cl, A Se/N, A C=N, A N–C–Se, deg. C–Se–Cl, deg.
1m
1d
PBE0
1.926
2.163
2.165
–
–
1.315
1.315
119.7
119.5
100.1
99.4
M06-2X 1.930
X-ray
PBE0
1.926(3)
1.923
2.4041(8) 2.141(3)
1.341(4) 116.8(2)
91.69(9)
99.1
2.286
2.261
2.371
2.458
–
1.331
1.329
116.7
116.3
M06-2X 1.932
94.2
2b
X-ray
1.9195(15) 2.3929(4)
2.4566(4)
1.344(2) 118.91(12)
89.21(5)
89.35(5)
93.2
M06-2X 1.919
2.326
2.566
–
1.346
117.6
88.8
˚
short NÁÁÁN contact of *2.8 A can be regarded as a
topological artifact due to nearly convergence of two ring
critical points (3; ?1) with the bonding critical point (3;
-1), which is especially distinct in the molecular graph
calculated using the PBE0 functional. All expected bond-
ing critical points and paths are actually observed in the
monomer molecular graph 1m without extra intramolecular
Se/N interactions. Therefore, we may conclude that the
planar monomeric structure in 1m is exclusively due to a
partial double character of the Se–C bond therein. This
statement is evident from MO plots of HOMO[-5] and
HOMO[-6] (Fig. 8).
9
8
7
6
5
4
3
2
1
0
QTAIM analysis results for the adduct 2b including both
molecular graph and topological parameters are essentially
equivalent to those reported for a benzimidazole analogue
[30] except for a somewhat higher energy of the N–HÁÁÁCl
intramolecular bond (14.0 vs. *8 kcal/mol).
0
20 40 60 80 100 120 140 160 180
The Se–Cl bond energies in 1m, 1d, and 2b were also
estimated using the Espinosa-Lecompte correlation (see
Table 4), which enabled us to trace how this energy
changes upon the formation of extra contacts. In particular,
the dimerization of 1m into 1d results in a weakening of
the Se–Cl bond by *8 kcal/mol, whereas the hydrochlo-
ration affording the adduct 2b results in even more
prominent weakening by *12 kcal/mol. The observed
energy changes correlate well with respective bond length
changes.
Rotation angle, deg
Fig. 6 Potential energy surface (PES) scanning for [PyH]SeCl2 (2b)
along the rotational angle coordinate calculated at the M06-2x/6-
311??G(d,p) level
as estimated according to the Espinosa-Lecompte correla-
tion [37].
Furthermore, both bonding paths and critical points are
present between the ClÁÁÁH(C) and NÁÁÁN atomic pairs. The
1m
1d
2b
Fig. 7 Molecular graphs for 1m, 1d, and 2b calculated at the M06-2X/6-311?G(d,p) level. The critical points: red—bond (3; -1); yellow—ring (3; ?1)
123

Struct Chem
Table 4 QTAIM parameters
calculated at the M06-2X/6-
311?G(d,p) level
Bond critical points (3; -1)
q(r), a.u.
Dq(r), a.u.
?0.021017
v(r), a.u.
Econt, kcal(kJ)/mol
Monomer 1m
Se–Cl
?0.114997
-0.111411
34.96 (146.27)
Dimer 1d
Se–Cl
?0.096368
?0.044810
?0.011589
?0.014642
?0.041305
?0.098518
?0.044549
?0.058762
-0.087215
-0.034429
-0.007026
-0.010739
27.36 (114.47)
10.8 (45.19)
2.20 (9.20)
Se/N
HÁÁÁCl
NÁÁÁN
[PyH]SeCl2 2b
HÁÁÁCl(C)
Se–Cl
3.37 (14.10)
?0.018241
?0.085811
?0.050497
?0.054058
?0.066719
?0.053845
?0.083931
?0.071169
-0.011636
-0.072690
-0.044617
-0.039157
3.65 (15.27)
22.80 (95.40)
14.00 (58.58)
12.29 (51.42)
ClÁÁÁH(N)
Se–Clbonded
Ph
Cl
N+
Ph
Se
OMe
MeO
N+
Cl
Se
CH2Cl2
r.t.
Fig. 8 MO plots for 2b indicating a partial double-bond character of
Se–C bond
or 2b
1b
Cl
Cl
N+
NuH
Nu
Se
+
RSeX
SeR
O
R1
N+
O
R1
X = Cl,Br
Se
Scheme 2 Selenocyclization of olefins and acetylenes
Scheme 3 Heterocyclization reactions of 1b and 2b with alkenes in
methylene chloride
Reactivity studies
ring closure by the nitrogen atom from the reactant’s
organyl moiety, which is currently under further develop-
ment [18–20, 30, 38–42]. In particular, we have demon-
strated for the first time that the introduction of a moiety
bearing a nitrogenous base, i.e. pyridine, into the selenenyl
chloride structure enables a novel avenue in the olefin
selenation affording cyclization products with the pyridine
nitrogen atom responsible for the ring closure [39–42].
As we have shown earlier [39–42], the reaction of
selenenyl chloride 1b with different alkenes, including
styrene, 1-ethynyl-4-methoxybenzene, cyclopentene, and
3,4-dihydro-2H-pyran, in methylene chloride affords the
respective heterocyclization products via the ring closure
by the nucleophilic nitrogen atom of the reactant’s hetaryl
moiety (Scheme 3). This implies that the dimeric reactant
1b dissociates under reaction conditions into transient
monomeric species similar to pyridine-2-selenenyl
Selen-containing electrophilic reagents, in particular
organylselenenyls, are widely used in contemporary
organic synthesis for the functionalization of different
types of substances, such as unsaturated compounds
[12–14]. For instance, the selenocyclization of olefins and
acetylenes with the ring closure by nucleophilic fragments
of the unsaturated substrate has proven to be a powerful
and useful approach to the synthesis of heterocyclic com-
pounds. Nitrogen, oxygen, and other atoms can act as
internal nucleophiles in such cyclization processes
(Scheme 2).
Recently, we have proposed a novel approach to the
synthesis of chalcogen- and nitrogen-containing heterocy-
cles based on tandem addition–cyclization reactions of
chalcogen-centered electrophiles at multiple bonds with the
123

Struct Chem
3. Back TG, Moussa Z, Parvez M (2004) Phosphorus Sulfur Silicon
179:2569–2579
4. Ranganathan S, Muraleedharan KM, Vaish NK, Jayaraman N
(2004) Tetrahedron 60:5273–5308
5. Młochowski J (2008) Phosphorus Sulfur Silicon 183:931–938
chloride, which are actually responsible for the formation
of target heterocyclization product. Taking into account
data on self-transformation of 1b reported in this paper,
we performed additional studies on reactions of T-shaped
selenenyl dichloride 2b with alkenes in methylene chlo-
ride. These reactions yield condensed heterocyclic com-
pounds fully identical to aforementioned ones. Thus, it
becomes clear that in this case also the reaction is actu-
ated by the dissociation of 2b to generate highly reactive
monomeric pyridine-2-selenenyl chloride.
¨
6. Klapotke TM, Krumm B, Polborn K (2008) Z Anorg Allg Chem
634:1287–1290
7. Mukherjee AJ, Zade SS, Singh HB, Sunoj RB (2010) Chem Rev
110:4357–4416
8. Selvakumar K, Singh HB, Butcher RJ (2010) Chem Eur J
16:10576–10591
9. Drabowicz J, Midura WH, Krasowska D (2011) Selenium and
tellurium (1,2,3)-oxygen-containing acids and derivatives. In:
Rappoport Z (ed) The chemistry of organic selenium and tel-
lurium compounds. Wiley, New York, pp 1027–1082
10. Selvakumar K, Singh VP, Shah P, Singh HB (2011) Main Group
Chem 10:141–152
Conclusions
¨
11. Pollnitz A, Lippolis V, Arca M, Silvestru A (2011) J Organomet
Chem 696:2837–2844
In conclusion, we have prepared and structurally char-
acterized two new selenenyl chloride compounds, viz.,
dimeric pyridine-2-selenium chloride (1b) and H-bonded
complex of pyridinium-2-selenium dichloride with
DMFA (2bÁDMFA). The experimental and theoretical
data obtained (1) clearly explain the relatively high sta-
bility of 1b, (2) directly confirm the presence of the
propeller-like free rotation of the SeCl2 moiety around
the essentially ordinary C–Se bond in solutions of
T-shaped hetarylselenenyl dichlorides, (3) prove that the
transformation of hetarylselenenyl chlorides into
T-shaped hetarylselenenyl dichlorides in solution is
energetically favorable, and thus (4) contribute to
understanding of mechanism of the novel heterocycliza-
tion reaction. Furthermore, our results revealed that the
investigated selenenyl chlorides 1b and 2b can serve as a
source of difficult-to-obtain, unstable organoselenenyl
chlorides, which should open new opportunities for the
study of low-valent chalcogens.
12. Santi C, Santoro S (2012) In: Wirth T (ed) Organoselenium
chemistry: synthesis and reactions, 1st edn. Wiley, New York
13. Zade SS, Singh HB (2014) Synthesis of organoselenium com-
pounds. In: Rappoport Z, Liebman JF, Marek I, Patai S (eds) The
chemistry of organic selenium and tellurium compounds, vol 4.
Wiley, New York, pp 1–180
14. Santi C, Tidei
C (2014) Electrophilic selenium/tellurium
reagents: reactivity and their contribution to green chemistry. In:
Rappoport Z, Liebman JF, Marek I, Patai S (eds) The chemistry
of organic selenium and tellurium compounds, vol 4. Wiley, New
York, pp 569–656
15. Nakanishi W, Hayashi S, Hashimoto M, Arca M, Aragoni MC,
Lippolis V (2013) Recent advances of structural chemistry of
organoselenium and organotellurium compounds. In: Organic
selenium and tellurium. John Wiley & Sons, Ltd., New York
16. Borisov AV, Matsulevich ZhV, Fukin GK, Baranov EV (2010)
Russ Chem Bull 59:581–583
17. Toshimitsu A, Owada H, Terao K, Uemura S, Okano M (1984) J
Org Chem 49:3796–3800
18. Khrustalev VN, Matsulevich ZV, Lukiyanova JM, Aysin RR,
Peregudov AS, Leites LA, Borisov AV (2014) Eur J Inorg Chem
(22):3582–3586
19. Borisov AV, Matsulevich ZhV (2009) Chem Heterocycl Compd
45:884–885
20. Borisov AV, Matsulevich ZhV, Osmanov VK, Borisova GN,
Naumov VI, Mammadova GZ, Maharramov AM, Khrustalev VN,
Kachala VV (2012) Russ Chem Bull 61:91–94
Supplementary materials
21. Sheldrick GM (2003) SADABS, v. 2.03, Bruker/Siemens Area
Detector Absorption Correction Program, Bruker AXS, Madison,
Wisconsin
Full crystal data as CIFs and optimized geometry of the
most stable conformers of 1b and 2bÁDMFA are included
as electronic supplement.
22. Sheldrick GM (2008) Acta Crystallogr A 64:112–122
23. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA,
Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant
JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B,
Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada
M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M,
Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox
JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J,
Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R,
Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA,
Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels
AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Ragha-
vachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S,
Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P,
Komaromi I, Martin RL, Fox DJ, Keith T, AlLaham MA, Peng
CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B,
Acknowledgments The authors thank the Russian Foundation for
Basic Research (Grant No. 14-03-00914) and the Russian Academy of
Sciences in the framework of the program ‘‘Theoretical and experi-
mental study of chemical bonding and mechanisms of chemical
reactions and processes’’ for financial support of this work.
References
1. du Mont W-W, Kubiniok S, Peters K, von Schnering H-G (1987)
Angew Chem Int Ed Engl 26:780–781
¨
2. Klapotke TM, Krumm B, Mayer P, Piotrowski H, Vogt M (2003)
Z Anorg Allg Chem 629:1117–1123
123

Struct Chem
Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03,
Revision E.01. Gaussian Inc, Wallingford
35. Husebye S, Lindeman SV, Rudd MD (1997) Acta Crystallogr
Sect C 53:809–811
24. Perdew JP, Burke K, Ernzerhof M (1997) Phys Rev Lett 78:1396
25. Zhao Y, Truhlar DG (2008) Theor Chem Acc 120:215–241
26. Krishnan R, Binkley JS, Seeger R, Pople JA (1980) J Chem Phys
72:650–654
36. Makarov AG, Makarov AYu, Bagryanskaya IYu, Shakirov MM,
Zibarev AV (2012) J Fluor Chem 144:118–123
37. Espinosa E, Molins E, Lecomte C (1998) Chem Phys Lett
285:170–173
27. McLean AD, Chandler GS (1980) J Chem Phys 72:5639–5648
28. AIMAll (Version 14.11.23), Keith TA (2014) TK Gristmill
Software, Overland Park KS, USA (aim.tkgristmill.com)
29. Cambridge Structural Database, Release 2016, Cambridge, UK.
30. Khrustalev VN, Ismaylova SR, Aysin RR, Matsulevich ZV,
Osmanov VK, Peregudov AS, Borisov AV (2012) Eur J Inorg
Chem (33):5456–5460
31. Minyaev RM, Orlova GV (1985) J Struct Chem 26:157–164
32. Demartin F, Devillanova FA, Isaia F, Lippolis V, Boyle PD,
Godfrey SM (2000) J Chem Soc Dalton Trans (12):1959–1960
33. Mammadova GZ, Matsulevich ZhV, Osmanov VK, Borisov AV,
Khrustalev VN (2012) Acta Crystallogr Sect E 68:o1381
34. Mammadova GZ, Matsulevich ZhV, Osmanov VK, Borisov AV,
Khrustalev VN (2011) Acta Crystallogr Sect E 67:o3050
38. Borisov AV, Osmanov VK, Borisova GN, Matsulevich ZV,
Fukin GK (2009) Mendeleev Commun 19(1):49–51
39. Borisov AV, Matsulevich ZV, Osmanov VK, Borisova GN,
Fukin GK (2010) 2-Pyridineselenenyl- and tellurenyl chlorides as
building blocks for derivatives of 2,3-dihydro[1,3]selen(tel-
lur)azolo[3,2-a]pyridin-4-ium. In: Nylund K, Johansson P (eds)
Heterocyclic compounds: synthesis, properties and applications.
Nova Science Publishers Inc, New York, pp 211–218
40. Borisov AV, Matsulevich ZhV, Osmanov VK, Borisova GN,
Savikhina EV (2007) Chem Heterocycl Compd 43:525–526
41. Borisov AV, Matsulevich ZhV, Tyurin YuM (2011) Chem
Heterocycl Compd 47:649–650
42. Borisov AV, Matsulevich ZhV, Osmanov VK, Borisova GN
(2012) Chem Heterocycl Compd 48:492–496
123