Electrophilic cyclization of homopropargyl tellurides: Synthesis and supramolecular structures of 2-aryl-3-iodo-1-phenyl-tellurophenium iodides and polyiodides

Article abstract of DOI:10.1016/j.poly.2014.02.013

The synthesis of five new 2-aryl-3-iodo-1-phenyl-tellurophenium iodides and polyiodides via electrophilic cyclization of homopropargyl tellurides using I₂ as an electrophile is described. The homopropargyl tellurides 1a and 1b react with differ

Full text of DOI:10.1016/j.poly.2014.02.013

Polyhedron 73 (2014) 45–50
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Polyhedron
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Electrophilic cyclization of homopropargyl tellurides:
Synthesis and supramolecular structures of
2-aryl-3-iodo-1-phenyl-tellurophenium iodides and polyiodides
a
a
b,
Roberta Cargnelutti a, , Ernesto S. Lang , Davi F. Back , Ricardo F. Schumacher
⇑
⇑
a Departamento de Química, Laboratório de Materiais Inorgânicos, Universidade Federal de Santa Maria, 97105-900 Santa Maria, RS, Brazil
b LASOL, CCQFA, Universidade Federal de Pelotas, UFPel, PO Box 354, 96010-900 Pelotas, RS, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
The synthesis of five new 2-aryl-3-iodo-1-phenyl-tellurophenium iodides and polyiodides via
electrophilic cyclization of homopropargyl tellurides using I2 as an electrophile is described. The
homopropargyl tellurides 1a and 1b react with different amounts of molecular iodine to give [C16H14TeI]I
(2), [C16H14TeI]I3 (3), {[C16H14ITe]4[I3À]3[IÀ]Á2I2} (4), [C17H16OTeI]I (5), and [C17H16OTeI]I3 (6). All of these
compounds display inter and/or intramolecular secondary interactions between TeÁ Á ÁI and/or IÁ Á ÁI in the
solid state, and these interactions are responsible for the formation of various supramolecular assemblies.
Ó 2014 Elsevier Ltd. All rights reserved.
Received 29 November 2013
Accepted 11 February 2014
Available online 19 February 2014
Keywords:
Electrophilic cyclization
Tellurophenium iodides and polyiodides
Supramolecular assemblies
1. Introduction
by the presence of an electrophilic source, such as iodine, copper
halides, and ArSeBr, represents an important protocol for the prep-
Tellurium is a versatile metalloid that is commonly used as a
base for several important materials, including catalysts and semi-
conductors, and it is used to prepare synthetic intermediates in or-
ganic synthesis that enable the introduction of various functional
groups [1–8]. Among these compounds, organotellurium(II) deriv-
atives and vinylic tellurides in particular provide powerful inter-
mediates for the synthesis of more elaborate alkenes, such as
natural products [6]. Many organotellurium(IV) compounds with
different ligands have been prepared and studied to date [9–12].
Tellurium(IV) iodides are of great interest because they can
promote structural diversity due to the tellurium geometry. In
the solid state, Te and I atoms interact strongly to form inter-
and intramolecular secondary interactions through the stereo-
chemically active lone pair at the Te center. These interactions
enable the formation of supramolecular networks. In the context
of supramolecular chemistry, all possible combinations of second-
ary interactions are important for creating dimers and polymeric
chains that form 1D, 2D, and 3D networks of the tellurium iodides
[13–18].
aration of highly substituted heterocycles [19]. The mechanism
underlying this reaction involves the coordination of an electro-
phile to the
p C–C bond of the alkyne, followed by the nucleophilic
anti-attack of the non-ligand heteroatom electron pair to the acti-
vated unsaturated C–C bond to give the heterocycle [19]. Inspired
by this reaction, our recent success in this area [20], and continuing
interest in the synthesis and applications of chalcogenophenes
[21–24], we envisioned the preparation of dihydrotellurophenium
iodides 2–6 using 1-arylltelluro-3-alkynes 1 and molecular iodine
as an electrophilic source (Scheme 1).
We report here the synthesis of five new 2-aryl-3-iodo-1-
phenyl-tellurophenium iodides and polyiodides via the electro-
philic cyclization of homopropargyl tellurides using I2 as an elec-
trophile. The products (2–6) were obtained in the presence of 1,
2, or 3 equiv. I2 in CH2Cl2/THF at room temperature and under inert
conditions. In all compounds, [C16H14TeI]I (2), [C16H14TeI]I3 (3),
{[C16H14ITe]4[IÀ3 ]3[IÀ]Á2I2} (4), [C17H16OTeI]I (5) and [C17H16OTeI]I3
(6), the tellurium atom is present in the oxidation state +4.
Initially, we focused our study on the synthesis of the homo-
propargyl tellurides 1 using homopropargyl tosylates and diaryl
ditellurides. The arylltellurolate anion, generated in situ by the
reaction of diaryl ditelluride with NaBH4 in THF/EtOH, reacted with
a solution of the homopropargyl tosylate in THF at room tempera-
ture and under an inert atmosphere for 6 h via a SN2 reaction
[25,26]. The homopropargyl tellurides 1a and 1b are shown in
Scheme 2 and were obtained in good yields.
On the other hand, the electrophilic cyclization of alkynes
containing a nucleophile near to the triple bond, which is activated
⇑
Corresponding authors. Tel.: +55 53 32757356; fax: +55 53 3275 7533.
E-mail addresses: rocargnelutti@yahoo.com.br (R. Cargnelutti), ricardo.schumacher@
ufpel.edu.br (R.F. Schumacher).
http://dx.doi.org/10.1016/j.poly.2014.02.013
0277-5387/Ó 2014 Elsevier Ltd. All rights reserved.

46
R. Cargnelutti et al. / Polyhedron 73 (2014) 45–50
-
I
In
I2
Ph Te
I
Ph Te
R
CH2Cl2/THF
Te
+
R
Ph
2 6
R
1
A
-
Scheme 1. General synthesis of dihydrotellurophenium iodides 2–6.
atom, once that these compounds are unable to undergo a SN2
reaction (Schemes 1 and 4).
(PhTe)2 (0.5 equiv)
NaBH4 (1.25 equiv)
R
R
OTs
TePh
THF, EtOH, rt, 5h
1a-b
2. Experimental
1a
R = C6H5, 60% (
R = 2-CH3OC6H4, 75% (1b)
)
2.1. General
Scheme 2. Synthesis of homopropargyl aryltellurides 1a and 1b.
All manipulations were conducted under an Ar (argon) atmo-
sphere using standard Schlenk techniques and dry solvents. These
solvents were purified and dried according to literature procedures
[27]. Elemental analyses (CHN) were carried out using a VARIO EL
(Elementar Analysen systeme GmbH) analyzer. Infrared spectra
were measured using a Bruker Tensor 27 mid-IR spectrometer.
Melting points were determined on a Microquímica MQAPF-301
melting point apparatus and are uncorrected.
With the starting materials 1 in hand, we turned out our atten-
tion to the preparation of the dihydrotellurophenium iodides 2–6
via an electrophilic cyclization mechanism involving iodine as an
electrophilic source. The products are presented in Scheme 3. The
compounds 2–4 were prepared by reacting the homopropargyl
phenyltelluride 1a with 1, 2, or 3 equivalents of molecular iodine.
The compounds 5 and 6 were synthesized by the reactions of the
homopropargyl 2-methoxyphenyl telluride 1b with 1 or 2 equiva-
lents of I2 using THF/CH2Cl2 as solvent. All products obtained were
isolated by crystallizing the mother solution via slow evaporation
of the solvents.
It is important to note that the dihydrotellurophenium iodides
2–6 isolated in this work can be considered as intermediates of
an electrophilic cyclization reaction. The crucial step in many elec-
trophilic cyclization reactions [19] involves the removal of the car-
bonic group bonded to the heteroatom via a SN2 displacement
(step B). SN2 displacement proceeds in the presence of a nucleo-
phile to generate the expected heterocycle 7 and the co-product
8 (Scheme 4).
2.2. Preparation of [C16H14ITe]I (2)
To a solution of 0.083 g (0.25 mmol) 1a in 10 mL CH2Cl2 was
added 0.063 g (0.25 mmol) I2 dissolved in 10 mL THF. The
mixture was stirred for 3 h. The slow evaporation of the
orange solution gave yellow crystals of 2. Yield: 76% based on
1a. Properties: yellow crystalline substance. Melting point:
144 °C–145 °C. Elemental Anal. Calc. for C16H14I2Te (587.69) C,
32.70; H, 2.40. Found: C, 32.73; H, 2.29%. IR (KBr, cmÀ1): 3046
(w), 3011 (w), 2948 (w), 1601 (m), 1486 (m), 1475 (m), 1434
(m), 881 (m), 766 (m), 729 (s), 700 (s), 682 (m), 558 (w), 445
(w). High resolution ESI + MS (m/z) of [C16H14ITe]+: calc.:
462.9197, Found: 462.9207.
To avoid the formation of 7, we selected homopropargyl
tellurides having an aryl group directly bonded to the tellurium
I
[I3-]3[I-]⋅2I2
Te
I
O
4
(
- 67%)
4
I-
Te
)
i
H 4
v
q
C 6
u
e
I2 (3 equiv)
R = C6H5
O
H 3
1
(
I
2
C
-
I
2
5
(
- 72%)
=
I2 (1 equiv)
R = C6H5
R
I-
Te
R
Te
(1a-b)
R
I
2
=
(
2
2
(
- 76%)
2
e
q
-
C
u
I2 (2 equiv)
R = C6H5
H
i
v
3
O
)
I
C
O
6 H
4
-
Te
I3
I
-
Te
I3
6
(
- 76%)
(3 - 71%)
Scheme 3. The synthesis of compounds 2–6 were conducted using the starting material 1 (0.25 mmol) and different equivalents of molecular iodine in a CH2Cl2/THF solvent
at room temperature over 3 h.

R. Cargnelutti et al. / Polyhedron 73 (2014) 45–50
47
E
E
EX
Solvent
PhXn
+
X
E
R
R
R
PhY
PhY
Y
Ph
B
Y
+
Xn
7
8
R
Scheme 4. The hypothetical heterocycle 7 can not be formed in the reaction.
2.3. Preparation of [C16H14ITe]I3 (3)
2.49%. IR (KBr, cmÀ1): 3048 (w), 2936 (w), 2835 (w), 1659 (w),
1610 (m), 1482 (s), 1459 (m), 1433 (s), 1253 (s), 1109 (m), 1025
(m), 888 (m), 756 (s), 730 (s), 682 (m), 581 (w). High resolution
ESI + MS (m/z) of [C17H16IOTe]+: calc.: 492.9308, Found: 492.9303.
To a solution of 0.083 g (0.25 mmol) 1a in 5 mL CH2Cl2 were
added 0.127 g (0.50 mmol) I2 dissolved in 15 mL THF. The mixture
was stirred for 3 h. The slow evaporation of the dark red solution
gave red crystals of 3. Yield: 71% based on 1a. Properties: red crys-
talline substance. Melting point: 132 °C–133 °C. IR (KBr, cmÀ1):
3048 (w), 2937 (w), 2899 (w), 1594 (w), 1569 (w), 1485 (m),
1474 (m), 1436 (s), 1244 (m), 756 (s), 728 (s), 691 (s), 680 (s),
557 (w), 449 (w). High resolution ESI + MS of [C16H14ITe]+: calc.:
462.9197, Found: 462.9199.
2.6. Preparation of [C17H16IOTe]I3 (6)
To a solution of 0.091 g (0.25 mmol) 1b in 5 mL CH2Cl2 were
added 0.127 g (0.50 mmol) I2 dissolved in 15 mL THF. The mixture
was stirred for 3 h. The slow evaporation of the red solution gave
red crystals of 6. Yield: 76% based on 1b. Properties: red crystalline
substance. Melting point: 151 °C–152 °C. IR (KBr, cmÀ1): 2996 (w),
1619 (m), 1480 (m), 1427 (m), 1245 (s), 1110 (m), 1017 (m), 754
(s), 731 (s), 680 (m), 579 (w), 558 (w). High resolution ESI + MS
(m/z) of [C17H16IOTe]+: calc.: 492.9308, Found: 492.9308.
2.4. Preparation of {[C16H14ITe]4[IÀ3 ]3[IÀ]Á2I2} (4)
To a solution of 0.083 g (0.25 mmol) 1a in 5 mL CH2Cl2 were
added 0.190 g (0.75 mmol) I2 dissolved in 20 mL THF. The mixture
was stirred for 3 h. The slow evaporation of the red dark solution
gave dark red crystals of 4. Yield: 67% based on 1a. Properties: dark
red crystalline substance. Melting point: 122 °C–123 °C. IR (KBr,
cmÀ1): 3047 (w), 3012 (w), 2948 (w), 1618 (m), 1590 (w), 1573
(w), 1486 (m), 1434 (s), 1219 (w), 995 (m), 912 (w), 881 (w), 730
(s), 691 (s), 558 (w), 446 (w). High resolution ESI + MS (m/z) of
[C16H14ITe]+: calc.: 462.9197, Found: 462.9209.
2.7. Crystallography
Data collection was performed on a Bruker APEX II CCD area
detector diffractometer using graphite-monochromatized Mo K
a
radiation. The structure was solved by direct methods using SHELXS
[28] and refined on F2 using anisotropic temperature parameters
for all non-hydrogen atoms [29]. Hydrogen atoms were included
in the refinement during the calculation of the positions. Crystal
data and details of the data collection and refinement processes
are summarized in Table 1. Table 2 summarizes selected bond
distances and angles within the compounds 2–6.
2.5. Preparation of [C17H16IOTe]I (5)
To a solution of 0.091 g (0.25 mmol) 1b in 5 mL CH2Cl2 were
added 0.063 g (0.25 mmol) I2 dissolved in 10 mL THF. The mixture
was stirred for 3 h. The slow evaporation of the orange solution
gave yellow crystals of 5. Yield: 72% based on 1b. Properties: yel-
low crystalline substance. Melting point: 162 °C–163 °C. Elemental
Anal. Calc. for C17H16I2OTe: C, 33.05; H, 2.61. Found: C, 33.18; H,
3. Results and discussion
The DIAMOND [30] representations of compounds 2–6 are pre-
sented in Figs. 1–6, and the crystallographic data are shown in
Table 1
Crystallographic data and refinement parameters for 2, 3, 4, 5, and 6.
Crystal Data
2
3
4
5
6
Formula
C
16H14I2Te
C16H14I4Te
841.47
293(2)
C64H56I18Te4
3619.69
293(2)
monoclinic
C2/m
27.452(1)
16.167(8)
9.93
90
93.032(2)
90
4400.8(4)
2
2.732
C17H16I2OTe
617.70
293(2)
monoclinic
P21/n
12.329(4)
11.667(4)
13.308(4)
90
104.85(1)
90
1850.6(1)
4
C17H16I4OTe
871.50
293(2)
monoclinic
P21/c
12.560(3)
9.595(3)
18.395(4)
90
91.09(1)
90
2216.5(1)
4
Formula weight (g molÀ1
)
587.67
296(2)
monoclinic
P21/n
12.325(5)
11.301(5)
13.031(5)
90
103.954(3)
90
1761.4(1)
4
T (K)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
triclinic
ꢀ
P1
9.553(4)
9.776(4)
13.527(6)
98.682(2)
101.066(2)
118.794(2)
1042.04(8)
2
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (g cmÀ3
)
2.216
5.181
2.682
7.346
2.217
4.941
2.612
6.915
l
(Mo K
a
) (mmÀ1
)
7.660
k/Å
F (000)
0.71073
1072
0.71073
748
0.71073
3204
0.71073
1136
0.71073
1560
Collected reflections
Unique reflections
20724
5394
1.100
0.0370
0.0427
17067
4595
1.074
0.0854
0.2840
28962
5076
1.050
0.0504
0.1518
57418
5228
1.031
0.0444
0.0922
15680
6054
1.028
0.0490
0.1200
Goodness-of-fit (GOF) (F2)
a
R1
b
wR2
P
P
a
IIF IÀIF II
IFI.
R1
=
/
c
0
0
P
P
b
wR2 = { w(F02 À Fc2)2/ w(F20)2}1/2
.

48
R. Cargnelutti et al. / Polyhedron 73 (2014) 45–50
Table 2
Selected bond lengths (Å) and angles (°) for the compounds 2–6.
2
3
4
5
6
Bond lengths
Te1Á Á ÁI2#2
Te1Á Á ÁI2#3
Te(1)–C(1)
Te(1)–C(16)
Te(1)–C(13)
Bond lengths
Te1Á Á ÁI2
Bond lengths
Te1Á Á ÁI6
Bond lengths
Te1Á Á ÁI2
Bond lengths
Te1Á Á ÁO1
3.6564 (1)
3.3477(1)
2.113(4)
2.113(5)
2.159(5)
3.6397(1)
3.9908(2)
2.902(2)
2.923(1)
2.09(1)
3.6945 (1)
3.7843(1)
3.5710(1)
3.6993(2)
3.6016(2)
3.3791(1)
3.7961(1)
3.1215(1)
3.3791(1)
2.119(6)
3.2427(1)
3.7539(1)
3.5020(1)
2.112(6)
2.125(6)
Te1Á Á ÁI4#1
I(3)–I(2)
Te1Á Á ÁI8#1
Te1Á Á ÁI9
Te1Á Á ÁI2#1
Te1Á Á ÁO1
Te1Á Á ÁI2#1
Te1Á Á ÁI4#2
Te–C(1)
I(3)–I(4)
I(1)–C(14)
I4Á Á ÁI2
Te1#1Á Á ÁI2#1
Te(1)–C(1)
I2Á Á ÁI5#1
Te–C(14)
Bond angles
Te–C(13)
Te–C(1)
Te–C(16)
Bond angles
I(2)–I(3)–I(4)
C(13)–Te–C(1)
C(13)–Te–C(16)
C(1)–Te–C(16)
1.94(1)
1.94 (1)
1.95(1)
Te–C(1)
Te–C(16)
Te–C(13)
I(7)–I(8)
I(7)–I(6)
I(3)–I(2)
I(4)–I(5)
Bond angles
C(1)–Te–C(16)
C(1)–Te–C(13)
C(16)–Te–C(13)
I(8)–I(7)–I(6)
2.122(9)
2.13(1)
Te(1)–C(17)
Te(1)–C(14)
Bond angles
C(1)–Te(1)–C(17)
C(1)–Te(1)–C(14)
C(17)–Te(1)–C(14)
2.123 (7)
2.149(6)
Te–C(17)
I(3)–I(2)
I(3)–I(4)
Bond angles
C(1)–Te–C(14)
C(1)–Te–C(17)
C(14)–Te–C(17)
I(2)–I(3)–I(4)
2.140(5)
2.8625(7)
2.9937(7)
C(1)–Te(1)–C(16)
C(1)–Te(1)–C(13)
C(16)–Te(1)–C(13)
Te1Á Á ÁI2#2Á Á ÁTe1#1
98.5 (2)
95.7(2)
83.0(2)
2.139(9)
2.834(1)
2.998(1)
2.893(1)
2.746(6)
98.2(3)
94.0(2)
82.2(3)
96.562(1)
178.90(5)
101.5(6)
88.9(6)
96.0(2)
97.1(2)
83.2(2)
174.81(2)
100.1(6)
96.6(4)
96.1(4)
84.0(4)
177.84(5)
charge of the iodide anion. The Te(IV) atom assumes a pyramidal
geometry due to the influence of the lone pair of electrons. This fig-
ure also shows the pseudodimeric structure of compound 2. The
pseudodimer is stabilized by secondary intermolecular interac-
tions (identified by dashed lines) between Te1Á Á ÁI2#2: 3.6564
(1) Å, Te1Á Á ÁI2#3: 3.3477 (1) Å and Te1#1Á Á ÁI2#2: 3.3477 (1) Å,
Te1#1Á Á ÁI2#3: 3.6564 (1) Å.
The complex 3 is illustrated in Fig. 2. In this compound, the an-
ion IÀ3 balances the charges of the [C16H14ITe]+ cation, and the I3–I2
distance is 2.902 (2) Å, I3–I4 is 2.923 (1) Å, and the angle I2–I3–I4
is 178.90 (5)°. Compound 3 form a pseudodimer via intermolecular
secondary interactions linking [C16H14ITe]+ to I3À. The following dis-
tances were measured: Te1Á Á ÁI2: 3.6397 (1) Å, Te1Á Á ÁI4#: 3.9908
(2) Å, Te1#1Á Á ÁI4: 3.9908 (2) Å, Te1#1Á Á ÁI2#: 3.6397 (1) Å. The sec-
ondary interactions of this compound induce the tellurium atom to
adopt a distorted square pyramidal geometry.
Fig. 3 shows the molecular structure of compound 4. For each
four cationic unit of [C16H14ITe]+ there are three I3À anions, one IÀ
anion and two neutral I2 molecules {[C16H14ITe]4[IÀ3 ]3[IÀ]Á2I2}. In
the solid state, complex 4 forms secondary interactions between
Te1Á Á ÁI6: 3.6945 (1) Å, Te1Á Á ÁI8#1: 3.7843 (1) Å, and Te1Á Á ÁI9:
3.5710 (1) Å. These secondary interactions induce the tellurium
atom to adopt a distorted octahedral geometry (Fig. 4). Fig. 4 shows
a three-dimensional chain formed by compound 4 in which the
unit of the [C16H14ITe]+ cation is connected by secondary interac-
tions with the IÀ3 anion. The center of this supramolecular structure
Fig. 1. DIAMOND [30] representation of the pseudodimeric structure of compound
2, achieved through TeÁÁÁI secondary interactions (represented by dashed lines).
Symmetry code: #1: Àx, 1 À y, Àz; #2: À1 + x, y, À1 + z; #3: 1 À x, 1 À y, 1 À z.
Hydrogen atoms have been omitted for clarity.
Table 1. The bonds and angles of the corresponding compounds are
listed in Table 2.
Fig. 1 shows the pseudodimeric structure of compound 2. The
formed product is an ionic compound in which the tellurium atom
is positively charged and is counterbalanced by the negative
Fig. 2. Pseudodimeric structure of compound 3, formed via TeÁ Á ÁI secondary interactions (represented by dashed lines). Symmetry code: #1: Àx, Ày, Àz. For clarity, the
hydrogen atoms are not shown.

R. Cargnelutti et al. / Polyhedron 73 (2014) 45–50
49
Fig. 5. A pseudodimer of compound
5
was formed through TeÁ Á ÁI secondary
interactions (represented by dashed lines). Symmetry code: #1: 1 À x, Ày, 2 À z.
Hydrogen atoms have been omitted for clarity.
tion of a pseudodimer occurs with secondary intermolecular
interactions between Te1Á Á ÁI2, Te1#1Á Á ÁI2#1 {3.3791 (1) Å} and
Te1Á Á ÁI2#1, Te1#1Á Á ÁI2 {3.7961 (1) Å}.
In addition to these interactions, the pseudodimer 5 forms two
more intramolecular interactions between Te1Á Á ÁO1 and
Te1#1Á Á ÁO1#1 {3.1215 (1) Å}. The secondary interactions around
the Te(IV) atom induces the adoption of a distorted octahedral
geometry (Fig. 5).
Fig. 6 shows the one-dimensional assembly of complex 6 in the
ab plane. This pseudopolymer is formed by inter and intramolecu-
lar secondary interactions that connect the [C17H16IOTe]+ cation
unit to the IÀ3 anion. In this complex, the Te(IV) atom assumes a
distorted octahedral geometry in the presence of the secondary
interactions. The distances of the various interactions are Te1Á Á ÁO1:
3.2427 (1) Å, Te1Á Á ÁI2#1: 3.7539 (1) Å, and Te1Á Á ÁI4#2: 3.5020
(1) Å.
Fig. 3. Molecular structure of compound 4. The distance between Te1Á Á ÁI9 is 3.5710
(1) Å. Symmetry code: #1: 1 À x, y, 1 À z; #2: x, Ày, z; #3: 1 À x, Ày, 1 À z. Hydrogen
atoms have been omitted for clarity.
includes one chain of polyiodides formed by secondary interac-
tions between I–IÁ Á ÁI–I, as in I3–I2Á Á ÁI4–I5:3.6993 (2) Å.
In the solid state, compound [C17H16IOTe]I (5) assumes a struc-
ture similar to that of the compound [C16H14ITe]I (2). The forma-
Fig. 4. Representation of the three-dimensional chain formed by the compound 4 through TeÁ Á ÁI and I–IÁ Á ÁI–I secondary interactions. Symmetry code: #1: x, y, À1 + z; #2:
1 À x; y; 1 À z; #3: 1 À x; Ày; 1 À z; #4: x, Ày, z. For clarity, the hydrogen atoms are not shown.

50
R. Cargnelutti et al. / Polyhedron 73 (2014) 45–50
Fig. 6. DIAMOND [30] representation of the unidimensional assembly of complex 6 in the ab plane. Symmetry code: #1: x, À1 + y, z; #2: Àx, À0.5 + y, 1.5 À z. For clarity, the
hydrogen atoms are not shown.
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4. Conclusions
In this work, the dihydrotellurophenium iodides 2–6 were
synthesized in good yields by the electrophilic cyclization of homo-
propargyl tellurides using I2 as an electrophile. The dihydrotellur-
ophenium iodides 2–6 are ionic compounds bearing a cationic
tellurium atom with an oxidation state of +4. The molecular iodine
played a crucial role in the formation of different products and,
depending on the stoichiometry of the iodine, different molecular
arrangements were observed. In this way 1 equiv. I2 yielded com-
pounds 2 and 5, which formed a dimeric chain in the solid state
with I– as counterions. The use of more than 1 equiv. I2 induced
the formation of polyiodides, such as the IÀ3 anion (compounds 3,
4, and 6). The synthesized compounds form, in the solid state, inter
and/or intramolecular secondary interactions between TeÁ Á ÁI and/
or IÁ Á ÁI, and these interactions are responsible for the formation
of various supramolecular assemblies.
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Acknowledgments
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This work was supported with funds from the Brazilian agen-
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Appendix A. Supplementary data
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CCDC 967560–967564 contains the supplementary crystallo-
graphic data obtained for compounds 2–6. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk.
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