A facile route for stabilizing highly reactive artecl species through the formation of T-Shaped tellurenyl chloride adducts: Quasi-planar zwitterionic [HPy]TeCl2 and [HPm]TeCl2; Py? = 2-pyridyl, Pm? = 2-(4,6-dimethyl)pyrimidyl

Article abstract of DOI:10.1002/ejic.201402294

Two new stable T-shaped tellurenyl chloride adducts, viz., [HPy]TeCl₂ (1) and [HPm]TeCl₂ (2) [Py? = 2-pyridyl, Pm? = 2-(4,6-dimethyl)pyrimidyl], act as close chemical analogs of highly unstable monomeric PyTeCl and PmTeCl. The quasi-

Full text of DOI:10.1002/ejic.201402294

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DOI:10.1002/ejic.201402294
A Facile Route for Stabilizing Highly Reactive
ArTeCl Species Through the Formation of T-Shaped
Tellurenyl Chloride Adducts: quasi-Planar Zwitterionic
[HPy*]TeCl2 and [HPm*]TeCl2; Py* = 2-pyridyl,
Pm* = 2-(4,6-dimethyl)pyrimidyl
Victor N. Khrustalev,*[a] Zhanna V. Matsulevich,[b]
Julia M. Lukiyanova,[b] Rinat R. Aysin,[a] Alexander S. Peregudov,[a]
Larissa A. Leites,[a] and Alexander V. Borisov[b]
Keywords: Tellurium / Multinuclear NMR spectroscopy / IR spectroscopy / Raman spectroscopy / X-ray diffraction /
Quantum chemistry
Two new stable T-shaped tellurenyl chloride adducts, viz.,
[HPy*]TeCl2 (1) and [HPm*]TeCl2 (2) [Py* = 2-pyridyl, Pm*
= 2-(4,6-dimethyl)pyrimidyl], act as close chemical analogs
of highly unstable monomeric Py*TeCl and Pm*TeCl. The
quasi-planar zwitterionic structures of 1 and 2 have been
studied by experimental (X-ray diffraction, multinuclear
NMR, IR and Raman spectroscopy) and theoretical (DFT and
QTAIM) methods. Thus, a novel facile route to stabilize
highly reactive Ar*TeCl species (Ar* = N-functionalized aryl)
by the addition of a hydrochloric acid molecule has been
demonstrated.
Introduction
Recently, we reported a new possibility for stabilizing
highly reactive organoselenenyl(II) chlorides by N-function-
alization of an organyl substituent and the subsequent
addition of a hydrochloric acid molecule.[1] It is well-known
that organotellurenyl(II) chlorides are even less stable
than the related organoselenenyl(II) chlorides. This fact
prompted us to apply the same approach to organotelluren-
yl(II) chlorides containing an N-functionalized aryl substit-
uent. The main purpose of the present investigation was to
expand this new stabilization route found for synthetically
important RSeCl species to their tellurium congeners.
To this end, we treated di(2-pyridyl) ditelluride[2] and
bis(4,6-dimethyl-2-pyrimidyl) ditelluride[3] with sulfuryl
chloride in dichloromethane at room temperature to pre-
pare the desired T-shaped aryltellurenyl(II) dichlorides 1
and 2 (Scheme 1).
Scheme 1. Reaction of di(2-pyridyl) ditelluride or bis(4,6-dimethyl-
2-pyrimidyl) ditelluride with sulfuryl chloride.
methane have been observed previously.[4] As expected, the
aryltellurenyl(II) dichlorides 1 and 2 obtained are quite
stable both in solution and the solid state. Their structures
and properties were further investigated in detail by dif-
ferent experimental and theoretical methods.
These reactions proceed through the formation of the
corresponding transient [ArTeCl] aryltellurenyl chlorides to
which a hydrochloric acid molecule, detached from the
CH2Cl2 solvent, then adds. Similar properties of dichloro-
Results and Discussion
Complexes 1 and 2 are orange substances and are quite
stable both in solution and the solid state at room tempera-
ture in air. They are highly soluble in dimethyl sulfoxide
(DMSO), poorly soluble in dichloromethane and chloro-
form, and insoluble in apolar solvents. They gave satisfac-
tory microanalytical and NMR spectroscopic data.
[a] A. N. Nesmeyanov Institute of Organoelement Compounds,
28 Vavilov Str., Moscow, 119991, Russian Federation
E-mail: vkh@xray.ineos.ac.ru
www.ineos.ac.ru
[b] R. E. Alekseev Nizhny Novgorod State Technical University,
Minin St., 24, Nizhny Novgorod, 603950 Russian Federation
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201402294.
X-ray diffraction analyses of 1 and 2 were undertaken to
establish their nature. The analyses revealed that both 1 and
2 attain the 10-E-3 T-shaped hypervalent chalcogen adduct
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configurations. The molecular structures of 1 and 2 along TeCl2 (Py* = 4-pyridyl).[6] It is noteworthy that, in contrast
with the atomic numbering schemes and selected geometric to 1 and 2, the T-shaped adduct [HPy*]TeCl2 was obtained
parameters are shown in Figure 1 and Figure 2.
by the direct reaction of di(4-pyridyl) ditelluride with HCl.
The Cl2 atoms in both 1 and 2 are also involved in the
intermolecular secondary Te···Cl interactions [Te1···Cl2
(–x, –½ + y, ½ – z) 3.4744(7) Å for 1 and Te1···Cl2 (–x, 1 –
y, 1 – z) 3.4602(10) Å for 2]. Thus, the tellurium atoms in
both 1 and 2 adopt a distorted square-planar coordination.
Due to the intermolecular Te···Cl interactions, molecules of
1 form chains along the crystallographic b axis, whereas
molecules 2 form almost planar centrosymmetric dimers.
As a result of intramolecular and intermolecular interac-
tions, the TeCl2 moieties in 1 and 2 have asymmetric geome-
tries with the Te–Cl2 bonds [2.6106(7) Å in 1 and
2.6684(10) Å in 2] being longer than the Te–Cl1 bonds
[2.5207(7) Å in 1 and 2.4641(9) Å in 2]. The mean values of
the two Te–Cl bond lengths in 1 [2.5657(7) Å] and 2
[2.5663(10) Å] are significantly larger than those in the two-
coordinate supermesityl-tellurenyl(II) chloride 2,4,6-
tBu3C6H2TeCl [2.384(1) Å].[7]
Figure 1. Molecular structure of 1. Thermal ellipsoids are shown
at the 50% probability level. The dashed line corresponds to the
intramolecular N1–H1···Cl2 hydrogen bond. Selected bond lengths
[Å] and angles [°]: Te1–Cl1 2.5207(7), Te1–Cl2 2.6106(7), Te1–C2
2.140(3), N1–C2 1.352(3), N1–C6 1.350(4), C2–C3 1.391(4), Cl1–
Te1–Cl2 177.29(2), Cl1–Te1–C2 90.26(7), Cl2–Te1–C2 87.13(7),
Te1–C2–N1 118.3(2), Te1–C2–C3 124.3(2), N1–C2–C3 117.4(2).
We have demonstrated by means of 77Se NMR spec-
troscopy that, for the planar benzothiazole-2-selenenyl di-
chloride in DMSO solution, propeller-like free rotation of
the SeCl2 moiety around the C–Se bond takes place due to
the cleavage of the intramolecular hydrogen bond.[1] As-
suming that an analogous dynamic process could occur in
Figure 2. Molecular structure of 2. Thermal ellipsoids are shown
at the 50% probability level. The dashed line corresponds to the
intramolecular N1–H1···Cl2 hydrogen bond. Selected bond lengths
[Å] and angles [°]: Te1–Cl1 2.4641(9), Te1–Cl2 2.6684(10), Te1–C2 solutions of 1 and 2, we performed variable-temperature
125Te NMR investigations of 1 in [D6]DMSO/CD2Cl2 solu-
2.138(3), N1–C2 1.346(5), N1–C6 1.347(4), C2–N3 1.318(4), N3–
C4 1.351(5), Cl1–Te1–Cl2 175.40(3), Cl1–Te1–C2 90.51(10), Cl2–
tion. The 125Te NMR spectra recorded at 298 and 253 K
Te1–C2 86.38(10), Te1–C2–N1 117.5(2), Te1–C2–N3 121.4(3), N1–
exhibit a single signal at δ = 1296 ppm and 1284 ppm,
C2–N3 121.1(3).
respectively, with the low-temperature signal demonstrating
Both structures are essentially zwitterionic, a negative a characteristic upfield shift (see Supporting Information).
charge resides on the TeCl2 moiety and a positive charge is
Remarkably, the tellurium signal, substantially broad-
delocalized over the heteroarene system. The C–Te dis- ened at 298 K (Δν1/2 = 220 Hz), becomes twice as narrow
tances of 2.140(3) Å in 1 and 2.138(3) Å in 2 are character- at 253 K (Δν1/2 = 110 Hz). This observation unambiguously
istic of single bonds [cf. previously reported lengths of proves the presence of the propeller-like dynamic process in
C=Te double bonds are 2.042(3)–2.087(3) Å].[5] The N1–C2 the solution of 1, which can be frozen out on temperature
and N1–C6 bond lengths in both compounds are equal due decrease and, consequently, clearly confirms the zwitter-
to the aromaticity of the cyclic systems.
ionic nature of 1 and 2 with the ordinary character of the
The virtually linear Cl–Te–Cl moieties in 1 [177.29(2)°] central C–Te bonds. The calculated values of the rotational
and 2 [175.40(3)°] lie almost in the heteroaryl planes [dis- barriers (at the M05–2x level) are 10.2 kcalmol–1 and
placements of 4.7(1) and 9.3(2)° for 1 and 2, respectively]. 11.0 kcalmol–1 for 1 and 2, respectively (see Supporting In-
Similar to the structure of benzothiazole-2-selone-dichlor- formation).
ide,[1] the quasi-planar conformations observed for 1 and 2
Of particular interest is the manifestation in the IR spec-
can be explained by the absence of steric hindrance (a bulky trum of the strong intramolecular N–H···Cl hydrogen bond.
substituent in the 3-position of the aromatic six-membered The IR spectra of pyridinium salts with strong (ΔH ≈ 10–
ring) inhibiting the formation of a strong intramolecular 11 kcalmol–1) interionic N+–H···B– hydrogen bonds were
N1–H1···Cl2 hydrogen bond [N···Cl 3.008(3) Å, H···Cl studied and discussed by Iogansen and coworkers.[8,9] Esti-
2.24(4) Å, N–H···Cl 144(3)° for 1 and N···Cl 2.988(3) Å, mation of the H-bond strengths in 1 and 2 based on AIM
H···Cl 2.24 Å, N–H···Cl 139° for 2]. The formation of the results (see Supporting Information) yield values of 10.9
intramolecular N1–H1···Cl2 hydrogen bond leads to a de- and 12.7 kcalmol–1, respectively. These values are very close
crease in the Cl2–Te1–C2 bond angle in comparison with or even higher than those reported in refs.[8,9] Thus, we
the Cl1–Te1–C2 angle [87.13(7) vs. 90.26(7)° for 1 and could expect that the H-bonds in 1 and 2 should manifest
86.38(10) vs. 90.51(10)° for 2, respectively].
themselves in the IR spectra similarly. Indeed, the patterns
Noticeably, the quasi-planar conformation of T-shaped observed in the IR spectra of 1 and 2 strongly resemble
tellurenyl chloride adducts can be stabilized not only by that for the pyridinium salt of CHCl2COOH with ΔH =
strong intramolecular but also by strong intermolecular in- 10.3 kcalmol–1.[9] In the region below 2000 cm–1, the spec-
teractions, as observed in the case of zwitterionic [HPy*] tra exhibit a very broad and intense continuum of a compli-
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cated contour observed as a background under a series of due to crystal-field splitting, whereas the weak lines at 222
narrow skeletal bands. In the spectrum of 2 (Figure 3), this and 232 cm–1 belong to various deformational modes.
background has three broad “sub-maxima” due to Fermi-
For benzothiazole-2-selone dichloride, the structure of
resonance perturbations. Such a pattern is typical of strong which is very similar to those of 1 and 2, some contribution
hydrogen bonds.[9] Naturally, as described in ref.,[8,9] this of a “carbene-Lewis acid” resonance form, leading to a par-
broad continuum, corresponding to the νNH perturbed by tial Se–C bond doubling, was suggested.[1] To elucidate the
H-bond formation is absent in the Raman spectra.
contribution from the analogous resonance form into the
total structure of 1 and 2, the population and QTAIM[11]
analyses at the DFT level with the M05-2X functional were
performed. It is easy to see from Figure 5 that the lone pair
of the Te atom acts as a π donor towards the empty p or-
bital of the carbon atom (the corresponding molecular or-
bital is the HOMO for both 1 and 2). The HOMO involves
a 67–68% contribution from the p orbital of the Te atom,
20–25% from the p orbitals of the two chlorine atoms, and
only 1–2% from that of the C2 atom. Therefore, the contri-
butions from the “carbene–Lewis acid” resonance form
and, as a consequence, the π component in the Te–C inter-
action are negligible. Thus the rotational barrier around the
Te–C bond is determined only by the strength of the intra-
molecular N–H···Cl hydrogen bond.
Figure 3. IR spectrum of solid 2.
The presence, in 1 and 2, of the intramolecular H-bond
closing the five-membered ring involving one Cl atom,
makes the two Te–Cl bonds inequivalent and thus leads to
a change in the vibrational mechanics of the νTeCl stretches
compared, for example, with those of Me2TeCl2 (νsTeCl =
248 cm–1, νasTeCl = 281 cm–1).[10]
The νTeCl region 240–300 cm–1 in the Raman spectra of
solid 1 and 2 is given in Figure 4. Three lines can be ob-
served in this region for 1. The NCA results show that the
most intense line at 260 cm–1 is a mixed mode with signifi-
cant contribution from the symmetrical stretch of the TeCl2
moiety (νsTeCl2), the line at 270 cm–1 involves mostly the
free Te–Cl bond stretch (νTeClfree), and the line at 246 cm–1
corresponds to a deformational mode which is complex in
origin. The νTeClH-bond coordinate contributes mostly to
the mode at 185 cm–1 which shows itself as a strong Raman
line. The vibrational mode Eigenvectors of molecule 2 are
slightly different. As for 1, the νTeClH-bond vibration is a
Raman line at 184 cm–1. However, the line corresponding
to the νTeClfree appears as a doublet 289/282 cm–1, probably
Figure 5. Representations of the HOMO of the planar complexes 1
(left) and 2 (right) as calculated at the M05-2X/6-311++G(d,p),cc-
pVTZ-pp level.
Moreover, we have observed that the dimeric solid bis-
(2-pyridyltellurenyl chloride) [2-PyTeCl]2 reported by us
previously[12] is fully converted into 1H-pyridine-2-telluren-
yl(II) dichloride 1 in dichloromethane solution over 120 h.
Evidently, in dichloromethane solution, the dimeric [2-Py-
TeCl]2 dissociates into the transient [2-PyTeCl] monomers
to which a hydrochloric acid molecule, detached from the
solvent, then adds (Scheme 2). Hence, in dichloromethane
solution, the T-shaped adduct [HPy]TeCl2 rather than the
dimer [2-PyTeCl]2 built up by the intermolecular dative
TeǟN interactions occurs as the energetically favorable sta-
bilized form of 2-pyridyltellurenyl chloride.
Scheme 2. Transformation of dimeric 2-pyridyltellurenyl chloride
to compound 1 by reaction with dichloromethane.
It is interesting to note that the dimeric stabilized form
was not observed by us for 4,6-dimethyl-2-pyrimidyltellur-
enyl chloride apparently due to the steric reasons. The DFT
quantum-chemical calculations show that the change in the
Figure 4. Raman spectra of solid 1 (red) and 2 (blue).
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shifts in the H NMR and 13C NMR spectra were indirectly refer-
enced to TMS by the solvent signals. The assignment of the signals
in the 1H NMR and 13C NMR spectra was performed by 2D
COSY, HSQC and HMBC techniques on the basis of the Bruker
standard software library. Chemical shifts in the 125Te NMR spec-
tra were measured with Ph2Te2 as an external standard (δ =
420.8 ppm[14]) and referenced to Me2Te. The accuracy of chemical
shift measurements is Ϯ0.01 ppm (for 1H), Ϯ0.05 ppm (for 13C)
and Ϯ0.1 ppm (for 125Te). The Raman spectra in the region 100–
4000 cm–1 were recorded for the solid samples by using a LabRAM
300 Jobin–Yvon laser Raman spectrometer with an exciting He-Ne
laser line of 632.8 nm at 1 mW power. IR spectra were recorded on
a Nicolet Magna IR-750 FTIR spectrometer in KBr pellets in the
region 400–4000 cm–1. The chemical analyses were performed by
using a Carlo Erba EA1108 CHNS-O analyzer. All calculations
were performed with the Gaussian 03 program at the DFT level of
theory using the PBE, PBE0 and M05–2X functionals with the
aug-cc-pVTZ-pp and 6-311++G(d,p) basis sets for Te and all other
atoms, respectively. (For details, see Supporting Information).
1
Gibbs’ free energy for the 4,6-dimethyl-2-pyrimidyltellur-
enyl chloride dimerization reaction is positive and equal to
+3.37 kcalmol–1 whereas, in the case of the 2-pyridyltellur-
enyl chloride, the analogous value is negative and equal to
–11.64 kcalmol–1 (for details, see Supporting Information).
The reactivity of 1 and 2 towards alkenes was also
studied, namely styrene and norbornene. In acetonitrile,
similar to 2-pyridyltellurenyl chloride,[13] the reactions pro-
ceeded smoothly at 20 °C affording heterocyclization prod-
ucts 3–6 (Scheme 3).
1H-Pyridine-2-tellurenyl Dichloride (1): (A) A solution of SO2Cl2
(0.27 g, 2 mmol) in CH2Cl2 (50 mL) was added to a solution of
di(2-pyridyl) ditelluride (0.82 g, 2 mmol) in CH2Cl2 (50 mL) at
room temperature. After 120 h, the solvent was evaporated in
vacuo. The precipitate contained 1.1 g (100%) of an orange crystal-
line product, m.p. 195–197 °C. (b) Pyridine-2-tellurenyl chloride[11]
(0.12 g, 0.5 mmol) was dissolved in CH2Cl2 (100 mL) at room tem-
perature. After 120 h, the solvent was evaporated in vacuo. The
precipitate contained 0.138 g (100%) of an orange crystalline prod-
uct, m.p. 195–197 °C. C5H5Cl2NTe (277.60): calcd. C 21.62, H 1.80,
N 10.11; found C 21.57, H 1.99, N 10.22. 1H NMR (600 MHz,
[D6]DMSO, Me4Si, 298 K): δ = 7.86 (t, J = 7.2 Hz, 1 H, 5-H), 8.32
(dt, J = 7.8, J = 1.8 Hz, 1 H, 4-H), 8.70 (d, J = 8.4 Hz, 1 H, 3-H),
8.79 (dd, J = 6.0, J = 1.2 Hz, 1 H, 6-H) ppm. 13C NMR (150 MHz,
[D6]DMSO, Me4Si, 298 K): δ = 125.6 [4J13C,125Te = 163 Hz, C5],
137.5 [2J13C,125Te = 177 Hz, C3], 142.9 [1J13C,125Te = 517 Hz, C2],
144.0 [3J13C,125Te = 197 Hz, C6], 144.7 [3J13C,125Te = 161 Hz,
C4] ppm. 125Te NMR (126 MHz, [D6]DMSO, Ph2Te2, 298 K): δ =
1282 ppm.
Scheme 3. Reactions of 1 and 2 with alkenes in acetonitrile solu-
tions.
The formation of 3–6 can be considered as the polar
[3+2] cycloaddition of tellurenyl chlorides to double bonds.
The corresponding hetarenetellurenyl chlorides are appar-
ently generated in situ upon the dissociation of 1 and 2 with
the abstraction of hydrochloric acid.
In summary, a novel facile route for stabilizing highly
reactive Ar*TeCl species (Ar* = nitrogen-containing aryl)
by hydrochloric acid addition has been demonstrated, ex-
emplified by two new T-shaped tellurenyl chloride adducts,
viz. 1H-pyridine-2-tellurenyl-dichloride and 4,6-dimethyl-
4,6-Dimethyl-1H-pyrimidine-2-tellurenyl Dichloride (2): A solution
of SO2Cl2 (0.0675 g, 0.5 mmol) in CH2Cl2 (10 mL) was added to a
1H-pyrimidine-2-tellurenyl-dichloride. Their quasi-planar solution of bis(4,6-dimethyl-2-pyrimidyl) ditelluride[3] (0.234 g,
0.5 mmol) in CH2Cl2 (10 mL) at room temperature. After 1 h the
solvent was evaporated in vacuo. The precipitate contained 0.3 g
(100%) of an orange powder product, m.p. 155–157 °C.
C6H8Cl2N2Te (306.64): calcd. C 23.53, H 2.61, N 9.15; found C
23.23, H 2.73, N 9.25. 1H NMR (600 MHz, CD2Cl2, Me4Si,
298 K): δ = 2.75 (s, 6 H, 2CH3), 7.20 (s, 1 H, 4-H) ppm. 13C NMR
(150 MHz, CD2Cl2, Me4Si, 298 K): δ = 22.7 [br, 2CH3, C7, C8],
118.1 [CH, C5], 119.7 [v.br, 2C(CH3), C4, C6], 159.4 [C(Te), C2]
ppm.
zwitterionic structures with strong intramolecular N–H···Cl
hydrogen bonds have been evidenced by experimental (sin-
gle-crystal X-ray diffraction, multinuclear NMR, vi-
brational spectroscopy) and theoretical (DFT and QTAIM)
methods. Due to this structure, the studied heteroaryl tellu-
renyl dichlorides react with alkenes in a similar manner to
the corresponding monomeric tellurenyl chlorides affording
the same cycloaddition products. The described approach
to difficult-to-obtain, extremely unstable organotellurenyl
chlorides opens alluring prospects in the synthesis and
study of low-valent chalcogen compounds.
Reactions of 1 and 2 with Alkenes (General Procedure): A solution
of unsaturated compound (1 mmol) in acetonitrile (20 mL) was
added to a solution of tellurenyl dichloride (1 mmol) in acetonitrile
(20 mL) at 20 °C with stirring. After 48 h at 20 °C, the solvent was
evaporated in vacuo. Compounds 3–6 were obtained after
recrystallization of the crude products from dichloromethane.
Experimental Section
General Methods: All manipulations were carried out in air. The
commercially available solvents were purified by conventional
methods and distilled immediately prior to use. NMR spectra were
3-Phenyl-2,3-dihydro[1,3]tellurazolo[3,2-a]pyridine-4-ium Chloride
(3): The yield of yellow crystals was 97%, m.p. 172–174 °C.
C13H12ClNTe (345.30): calcd. C 45.22, H 3.50; found C 45.11, H
3.45. 1H NMR (600 MHz, [D6]DMSO, Me4Si, 298 K): δ = 3.80
(dd, J = 10.3, J = 7.3 Hz, 1 H, 2-H), 4.28 (dd, J = 10.3, J = 7.3 Hz,
recorded on Bruker AVANCE-600 (1H and 13C) and AVANCE-400
1
(
125Te) NMR spectrometers at 600.22 MHz (for H), 150.93 MHz
(for 13C) and 126.24 MHz (for 125Te) in [D6]DMSO. Chemical 1 H, 2-H), 6.60 (t, J = 7.3 Hz, 1 H, 3-H), 7.40 (m, 2 H, Ph), 7.48
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(m, 3 H, Ph), 7.78 (dd, J = 7.3, J = 5.9 Hz, 1 H, 6-H), 8.32 (t, J = CCDC-980195 (for 1) and CCDC-980196 (for 2) contain the sup-
7.3 Hz, 1 H, 7-H), 8.42 (d, J = 7.3 Hz, 1 H, 8-H), 8.52 (d, J = plementary crystallographic data for this paper. These data can be
5.9 Hz, 1 H, 5-H) ppm.
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
5,7-Dimethyl-3-phenyl-2,3-dihydro[1,3]tellurazolo[3,2-a]pyrimidine-
4-ium Chloride (4): The yield of yellow crystals was 75%, m.p. 122–
124 °C. C14H15ClN2Te (374.34): calcd. C 44.92, H 4.04; found C
Supporting Information (see footnote on the first page of this arti-
cle): Full crystal data, NMR, Raman and IR spectra and details
of the quantum-chemical calculations.
1
44.87, H 4.01. H NMR (600 MHz, [D6]DMSO, Me4Si, 298 K): δ
= 2.53 and 2.63 (s, 6 H, 2CH3); 3.19 (d, J = 11.7 Hz, 1 H, 2-H);
4.80 (dd, J = 11.7, J = 7.3 Hz, 1 H, 2-H); 6.75 (d, J = 7.3 Hz, 1 H, Acknowledgments
3-H); 7.20 (m, 2 H, Ph); 7.42 (m, 3 H, Ph); 7.64 (s, 1 H, 6-H) ppm.
The authors thank the Russian Foundation for Basic Research
exo-cis-9-Tellurium-3-azoniatetracyclo[9.2.1.02,10.03,8]tetradeca-
3(8),4,6-triene Chloride (5): The yield of yellow crystals was 95%,
m.p. 230–232 °C. C12H14ClNTe (335.30): calcd. C 42.99, H 4.21;
found C 42.88, H 4.15. 1H NMR (600 MHz, [D6]DMSO, Me4Si,
298 K): δ = 1.34 (d, J = 10.8 Hz, 1 H, Hsyn14), 1.39 (m, 1 H, 12-
H), 1.52 (m, 1 H, 12-H), 1.68 (d, J = 10.8 Hz, 1 H, Hanti14), 1.71
(m, 2 H, 13-H), 2.61 (s, 1 H, 11-H), 2.82 (s, 1 H, 1-H), 4.12 (d, J
= 8.4 Hz, 1 H, 10-H), 5.32 (d, J = 8.4 Hz, 1 H, 2-H), 7.70 (dd, J
= 7.5, J = 6.2 Hz, 1 H, 5-H), 8.01 (dd, J = 8.0, J = 7.5 Hz, 1 H,
6-H), 8.20 (d, J = 8.0 Hz, 1 H, 7-H), 8.93 (d, J = 6.2 Hz, 1 H, 4-
H) ppm. 13C NMR (150 MHz, CD2Cl2, Me4Si, 298 K): δ = 25.71
(C12), 29.41 (C13), 31.84 (C14), 32.84 (C10), 45.97 (C11), 48.16
(C1), 82.78 (C2), 123.99 (C5), 132.61 (C7), 141.45 (C6), 145.22
(C4) ppm.
(grant number 14-03-00914) and the Russian Academy of Sciences
in the framework of the program “Theoretical and experimental
study of chemical bonding and mechanisms of chemical reactions
and processes” for financial support of this work. Dr. Y. V. Zubav-
ichus is thanked for fruitful discussions.
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exo-cis-4,6-Dimethyl-9-tellurium-3-azonia-7-azatetracyclo-
[9.2.1.02,10.03,8]tetradeca-3(8),4,6-triene Chloride (6): The yield of
yellow crystals was 79%, m.p. 136–138 °C. C13H17ClN2Te (364.34):
calcd. C 42.86, H 4.70; found C 42.78, H 4.62. 1H NMR (600 MHz,
[D6]DMSO, Me4Si, 298 K): δ = 1.40 (m, 1 H, 12-H), 1.47 (d, J =
11.0 Hz, 1 H, Hsyn14), 1.60 (m, 1 H, 12-H), 1.81 (m, 2 H, 13-H),
2.10 (d, J = 11.0 Hz, 1 H, Hanti14), 2.52 and 2.75 (s, 6 H, 2CH3),
2.61 (s, 1 H, 11-H), 2.71 (s, 1 H, 1-H), 4.30 (d, J = 8.8 Hz, 1 H,
10-H), 5.22 (d, J = 8.8 Hz, 1 H, 2-H), 7.58 (s, 1 H, 5-H) ppm.
Crystal Data for 1 at 100 K: C5H5NCl2Te (Mr = 277.60), mono-
clinic, space group P21/c, a = 12.0195(9) Å, b = 7.0071(5) Å, c =
9.5895(7) Å, β = 104.071(1)°, V = 783.41(10) Å3, Z = 4, ρcalcd.
=
2.354 gcm–3, μ = 4.389 mm–1, Bruker SMART APEX-II CCD dif-
fractometer, graphite monochromator, λ(Mo-Kα) = 0.71073 Å. A
total of 9643 reflections were collected in the θ range of 1.75–30.00°
with 2274 being unique (Rint = 0.0375). A semi-empirical absorp-
tion correction was applied based on the intensities of equivalent
reflections (Tmin = 0.353, Tmax = 0.668). Least-squares refinement
on 85 parameters converged normally with R1 [I Ͼ 2σ(I)] = 0.0380
(2151 reflections), wR2 (all data) = 0.1039, GOF = 1.001.
Crystal Data for 2 at 100 K: C6H8N2Cl2Te (Mr = 306.64), mono-
clinic, space group P21/n, a = 6.5102(6) Å, b = 12.6556(12) Å, c =
11.8465(11) Å, β = 97.857(2)°, V = 966.88(16) Å3, Z = 4, ρcalcd.
= 2.107 gcm–3, μ = 3.570 mm–1, Bruker SMART APEX-II CCD
diffractometer, graphite monochromator, λ(Mo-Kα) = 0.71073 Å.
A total of 10218 reflections were collected in the θ range of 2.37–
27.96° with 2320 being unique (Rint = 0.0441). A semi-empirical
absorption correction was applied based on the intensities of equiv-
alent reflections (Tmin = 0.507, Tmax = 0.635). Least-squares refine-
ment on 102 parameters converged normally with R1 [I Ͼ 2σ(I)] =
0.0280 (1908 reflections), wR2 (all data) = 0.0584, GOF = 1.002.
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Received: April 9, 2014
Published Online: June 26, 2014
Eur. J. Inorg. Chem. 2014, 3582–3586
3586
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim