(Z)-diiodo(2-iodo-2-phenylvinyl)(phenyl)tellurium PhIC=CHTeI2Ph: Synthesis and complexing properties in a reaction with iron pentacarbonyl

Article abstract of DOI:10.1134/S1070328408110031

Electrophilic addition of PhTeI₃ to phenylacetylene (PhC ₂H) in boiling THF stereoselectively gave (Z)-diiodo(2-iodo-2- phenylvinyl)(phenyl)tellurium PhIC=CHTeI₂Ph (I). In a reaction with Fe(CO)₅, this complex easily eliminated two iodine atoms from tellurium to give PhTe-CH=CPhI. This ligand was coordinated to iron in a monodentate fashion through the Te atom in the resulting complex (CO) ₃FeI₂(PhTeHC=CPhI) (II). The reaction also yielded the known complex Fe(CO)₄I₂ (III). The structures of complexes I-III were determined by X-ray diffraction analysis. The Fe-Te bond in structure II is substantially shortened.

Full text of DOI:10.1134/S1070328408110031

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2008, Vol. 34, No. 11, pp. 805–810. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © Yu.V. Torubaev, A.A. Pasynskii, P. Mathur, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 812–816.
(Z)-Diiodo(2-iodo-2-phenylvinyl)(phenyl)tellurium
PhIC=CHTeI2Ph: Synthesis and Complexing Properties
in a Reaction with Iron Pentacarbonyl
Yu. V. Torubaeva, A. A. Pasynskiia, and P. Mathurb
a Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
b Indian Institute of Technology, Bombay, India
E-mail: hansmail@rambler.ru
Received June 4, 2008
Abstract—Electrophilic addition of PhTeI3 to phenylacetylene (PhC2H) in boiling THF stereoselectively gave
(Z)-diiodo(2-iodo-2-phenylvinyl)(phenyl)tellurium PhIC=CHTeI2Ph (I). In a reaction with Fe(CO)5, this com-
plex easily eliminated two iodine atoms from tellurium to give PhTe–CH=CPhI. This ligand was coordinated
to iron in a monodentate fashion through the Te atom in the resulting complex (CO)3FeI2(PhTeHC=CPhI) (II).
The reaction also yielded the known complex Fe(CO)4I2 (III). The structures of complexes I–III were deter-
mined by X-ray diffraction analysis. The Fe–Te bond in structure II is substantially shortened.
DOI: 10.1134/S1070328408110031
Aryltellurium trihalides ArTeX3 (X = Cl or Br) [1] (aryl)dihalo(halovinyl)tellurium(IV) [2, 3]. It has
obtained from stoichiometric amounts of diaryl ditel- been demonstrated that reflux of ArTeX3 with acety-
luride and elemental halogen have found use in lene can yield Z- and E-isomers, depending on the sol-
organic chemistry because of their tendency toward vent polarity. Further reduction with NaBH4 or
stereo- and regioselective electrophilic addition to the Na2S2O3 can afford the corresponding aryl halovinyl
triple C–C bond of terminal acetylenes, giving tellurides (Scheme 1):
R
R
Ar2Te2
X2
X
Te Ar
X
X
Te Ar
Benzene
~80°C
X
ArTeX3
X = Cl, Br
X
X
R
R
MeOH
65°C
X
R
X–
+
Te Ar
R
Te Ar
X
X
X
X
R
NaBH4/THF/EtOH
–5°C
X
Te Ar
X
Te Ar
X
X
X = Cl, Br
The behavior of aryltellurium triiodides in such phenylacetylene and reactions of the resulting
reactions has not been documented hitherto. According (aryl)diiodo(iodovinyl)tellurium(IV) with iron pentac-
to X-ray diffraction data, triiodo(phenyl)tellurium in arbonyl. The latter reactions could be assumed to be
the crystal forms dimers with bridging iodine atoms similar to a known oxidative addition of diiodo(diphe-
[4]. We found it interesting to study its reaction with nyl)tellurium(IV) to Fe(CO)5 [5]:
805

806
TORUBAEV et al.
C(5)
C(6)
C(4)
C(7)
C(14)
C(13)
C(3)
C(2)
C(9)
C(8)
C(1)
I(1)
C(12)
C(10)
C(11)
Te(1)
I(2)
I(3)
Fig. 1. Molecule IA in crystal structure I.
formed consisted of thick needles of complex II and
prisms of the known complex III [6].
Fe(CO)5
20°C, THF
Ph
I
Ph
Te I
Ph
Ph
Te
Fe
Below are the IR spectra and elemental analysis data
for complexes II and III.
OC
OC
I
I
IR (KBr, cm–1): 2125 s, 2085 s, 2070 s. IR (heptane,
CO
cm–1): 2125 m, 2075 s, 2060 m.
For C17H11TeI3O2Te(II) (M = 827.43)
EXPERIMENTAL
anal. calcd. (%):
C, 24.68;
H 1.34.
H 0.87.
All manipulations dealing with the synthesis and Found (%):
C, 20.88;
For C4FeI2O4(III) (M = 421.70)
anal. calcd. (%):
isolation of the complexes were carried out under pure
argon in dehydrated solvents. IR spectra were recorded
on a Specord 75IR spectrophotometer for pellets with
KBr and solutions in heptane.
C, 11.39.
The complexes are unstable under the conditions of
column chromatography. The crystals of complexes II
and III for X-ray diffraction analysis were selected by
mechanical separation.
Synthesis of PhTeI2HC=CPhI (I). Triiodo(phe-
nyl)tellurium (1.15 g, 2 mmol) (prepared from PhTe2
(0.4 g) and I2 (0.75 g)) and phenylacetylene (0.22 ml,
2 mmol) were refluxed in THF (30 ml) for 12 h. The
solvent was removed in a water aspirator vacuum. The
orange red residue was washed with light petroleum.
The product was extracted with CH2Cl2 and precipi-
tated by concentrating the extract with heptane in a
water aspirator vacuum. Crystals suitable for X-ray dif-
fraction analysis were grown from a concentrated solu-
tion of complex I in CH2Cl2–heptane (1 : 1).
X-ray diffraction analysis. Selected crystallo-
graphic parameters and a summary of data collection
and refinement for structures I–III are given in Table 1.
All structures were solved by the direct method and
refined by the least-squares method on F2 in the aniso-
tropic (for H atoms, isotropic) approximation with the
SHELXTL program package [7]. The hydrogen atoms
were located geometrically. Selected bond lengths and
angles in structures I–III are given in Tables 2 and 3.
Atomic coordinates and other structural parameters of
complexes I–III have been deposited with the Cam-
bridge Crystallographic Data Center (CCDC
nos. 688683 (I), 690063 (II), and 688684 (III); see
http://www.ccdc.cam.ac.uk/data_request/cif).
For C14H11I3Te (M = 687.55) anal. calcd. (%):
C, 24.46; H, 1.61.
Found (%): C, 24.70; H, 1.85.
IR (KBr, cm–1): 720 s, 680 s, 650 s.
Synthesis of (CO)3FeI2(PhTe–CH=CPhI) (II) and
Fe(CO)4I2 (III). Iron pentacarbonyl (0.04 ml,
0.28 mmol) was added in one portion at room tempera-
ture to a magnetically stirred orange red solution of
complex I (0.16 g, 0.23 mmol) in diethyl ether (30 ml).
RESULTS AND DISCUSSION
We carried out a reaction of PhTeI3 with phenylacet-
Stirring was continued for an additional 30 min. The ylene in boiling THF. More prolonged reflux was
reaction mixture turned deep red and homogeneous and required, in contrast to analogous reactions with
no longer contained the starting complex I (TLC data). (aryl)dibromotellurium(IV) and (aryl)dichlorotellu-
The solution was concentrated with heptane (5 ml) rium(IV) usually completed in 3–10 h. The resulting
in vacuo to slight turbidity. The concentrate was kept at dark orange crystals of the adduct were stable in air and
–10°ë for 12 h. The dark red crystalline precipitate that soluble in polar organic solvents. According to X-ray
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 11 2008

(Z)-DIIODO(2-IODO-2-PHENYLVINYL)(PHENYL)TELLURIUM
807
Table 1. Selected crystallographic parameters and a summary of data collection and refinement for structures I–III
Value
Parameter
I
II
III
Diffractometer
Radiation (λ, Å)
Temperature
Space group
a, Å
b, Å
c, Å
Bruker APEX II CCD
MoKα (0.71073)
296(2)
C2/c
P21/c
11.2403(5)
8.5755(4)
36.3256(17)
98.068(1)
3466.8(3)
8
C2/c
26.375(5)
10.0848(16)
17.701(3)
103.441(4)
4579.3(13)
8
7.078(2)
10.906(2)
12.633(3)
92.268(5)
974.4(4)
2
2.137
5.816
580
β, deg
V, Å3
Z
ρ(calcd), g/cm3
2.635
7.042
2448
2.400
5.964
2992
µ, mm–1
F(000)
θ scan range, deg
2.01–29.00
3.23–28.98
ω
1.59–29.00
Scan mode
Number of measured reflections
Number of independent reflec-
tions (N1)
37252
9193 = 0.0562)
3653
24582
6079 (Rint = 0.0300)
1277 (Rint = 0.0320)
Number of reflections with
I > 2(I) (N2)
5294
1076
4810
Number of parameters refined
GOOF (F2)
R1 for N2
325
0.973
0.0415
51
1.033
0.0264
226
1.023
0.0364
wR2 for N1
0.0919
1.326/–1.604
0.0686
0.871/–0.590
0.1006
1.926/–1.230
∆ρmax/ρmin, e Å–3
Table 2. Selected bond lengths and angles in the crystallo-
graphically independent molecules IA and IB of complex I
diffraction data, the adduct is the (Z)-isomer of
diiodo(2-iodo-2-phenylvinyl)(phenyl)tellurium(IV) (I):
Bond
d, Å
Bond
d, Å
IA
IB
PhTel3
reflux,
THF
I
Te
Te(1)–C(1)
2.109(6) Te(1A)–C(1A)
2.126(6) Te(1A)–C(10A)
2.9098(7) Te(1A)–I(1A)
2.9308(7) Te(1A)–I(2A)
1.310(8) C(1A)–C(2A)
2.110(6) C(2A)–I(3A)
2.097(6)
2.129(6)
2.8777(7)
2.9723(7)
1.299(8)
2.113(6)
I
I
Te(1)–C(10)
Te(1)–I(2)
Te(1)–I(1)
C(1)–C(2)
C(2)–I(3)
(I)
The unit cell of crystal structure I comprises two
crystallographically independent molecules IÄ (Fig. 1)
and IB. In their two sublattices, the Te–I distances are
2.9098(7)–2.9308(7) Å and 2.8777(7)–2.9723(7) Å.
These values are close to the sum of the covalent Te and
I radii [8] and to normal bond lengths in diorganotellu-
rium(IV) diiodides [4]. The Te···I distances differ only
slightly; this can be explained by the packing effect in
the crystal, viz., nonvalent Te···I and I···I interactions.
Independent molecules IA are united in the crystal
through the I(1)···Te(1) contacts (3.665(1) Å). Mole-
cules IB are linked by the Te(1A)···I(2A) contacts
Angle
ω, deg
Angle
ω, deg
(3.752(1) Å) into centrosymmetric dimers, which form I(2)Te(1)I(1) 178.14(2) I(1A)Te(1A)I(2A) 175.04(2)
chains via the I(1A)···I(3A) contacts (3.775(1) Å). It
should be noted that the interactions in chains differ in
both contact length and direction. For instance, the
angle C(1)Te(1)I(1) is 165.7(1)° for the chains of mole-
cules IA and 175.8° for molecules IB (Fig. 2).
C(2)C(1)Te(1) 124.3(5) C(2A)C(1A)Te(1A) 123.8(5)
C(1)C(2)I(3) 118.1(5) C(1A)C(2A)I(3A) 117.0(5)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 11 2008

808
TORUBAEV et al.
Table 3. Selected bond lengths and angles in structure II
tion data (the lengths of two cis-arranged Fe–I bonds
are 2.6375(6) Å) (Fig. 3).
Bond
d, Å
Replacement of another CO group in complex I by
in situ generated (Z)-2-iodo-2-phenylvinyl phenyl tel-
luride gives complex III. Its black red crystals are rela-
tively stable in air and soluble in most organic solvents.
III
Te(1)–C(1)
Te(1)–C(9)
C(1)–C(2)
C(2)–I(3)
2.100(5)
2.110(6)
1.325(7)
2.120(5)
2.6335(9)
2.6349(9)
2.5815(8)
Fe(CO)5
20°C, Et2O
I
Te
I
Te
Fe
I
I
Fe(1)–I(1)
Fe(1)–I(2)
Te(1)–Fe(1)
OC
OC
I
I
CO
(II)
(I)
According to X-ray diffraction data, the Te and I
atoms in complex III are in opposition to the carbonyl
groups (Fig. 4). The Fe–I distances (2.6335(9) and
2.6349(9) Å) correspond to the single bonds found in
the complexes (CO)3FeI2(L): e.g., 2.6482(7) and
2.6541(6) Å in (CO)3FeI2(Te2Ph2) (IV) or 2.6478(7) and
2.6541(7) Å in (CO)3FeI2(PhTeI) (V) [9]. At the same
time, the Te–Fe distance (2.5815(8) Å), as in complexes
IV and V, is substantially shorter than the sum of the
covalent Fe and Te radii (2.70 Å) [8]. This is probably
due to a dative interaction of the lone electron pairs on
the Fe atom with the vacant d orbital of the Te atom, in
addition to the donor–acceptor bonding between tellu-
rium and iron.
Angle
ω, deg
C(1)Te(1)C(9)
C(1)Te(1)Fe(1)
C(9)Te(1)Fe(1)
C(2)C(1)Te(1)
97.2(2)
103.35(14)
100.16(15)
126.1(4)
In a room-temperature reaction of complex I with
Fe(CO)5 in ether, two iodine atoms are transferred from
tellurium to iron with elimination of one CO group to
give the known complex Fe(CO)4I2 (II) [6]. It was iso-
Note that complexes II and III cannot be separated
by crystallization and are unstable under the conditions
of column chromatography. According to elemental
lated and structurally characterized by X-ray diffrac- analysis data, the ratio II : III is close to 30 : 70. Their
(‡)
(b)
I(1)'
I(1A)''
I(3A)
Te(1)
C(1)''
I(3A)''
C(1A)''
Te(1)''
I(1)
C(1)
I(2A)''
I(2)
Te(1A)
Te(1A)''
I(2A)
I(1A)
I(3)
C(1A)
Fig. 2. Molecular packing of (a) IA and (b) IB in crystal structure I.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 11 2008

(Z)-DIIODO(2-IODO-2-PHENYLVINYL)(PHENYL)TELLURIUM
809
O(1)
C(1)
O(2A)
C(2A)
I(1A)
Fe(1)
C(2)
O(2)
I(1)
C(1A)
O(1A)
Fig. 3. Molecular structure II (Fe(1)–I(1) 2.6375(6) Å, Fe(1)–C(2) 1.811(4) Å, Fe(1)–C(1) 1.850(4) Å, O(1)–C(1) 1.111(5) Å,
O(2)–C(2) 1.128(5) Å).
C(5)
I(3)
C(4)
C(6)
C(3)
C(12)
C(11)
C(2)
C(7)
C(10)
Te(1)
C(13)
C(8)
C(14)
O(2)
C(9)
C(1)
O(1)
C(15)
C(16)
Fe(1)
I(2)
I(1)
C(17)
O(3)
Fig. 4. Molecular structure III.
total IR spectrum is obviously a superposition of the 2047 cm–1) in hexane [6] and the spectrum of complex
known spectrum of complex II (2131, 2086, 2062, and III, which should be similar to the IR spectra of com-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 11 2008

810
TORUBAEV et al.
2. Zeni, G., Ludtke, D.S., Panatieri, R.B., and Braga, A.L.,
plexes IV and V in the range of CO stretching vibra-
tions (ν, cm–1: 2080 s, 2040 s, 2025 s [7]).
Chem. Rev., 2006, vol. 106, p. 1032.
3. Huang, X. and Wang, Y.-P., Tetrahedron Lett., 1996,
vol. 37, p. 7417.
ACKNOWLEDGMENTS
4. Alcock, N.W. and Harisson, W.D., J. Chem. Soc., Dalton
Trans., 1984, p. 869.
This work was supported by the Russian Foundation
for Basic Recearch (project no. 06-03-32891), the Divi-
sion of the Chemistry and Materials Sciences of the
Russian Academy of Sciences (grant no. OKh 1.5), and
the RAS Presidium (project no. 8P15).
5. Liaw, W.-F., Chiang, M.-H., Lai, C.-H., et al., Inorg.
Chem., 1994, vol. 33, p. 2493.
6. Brauer, G. Handbook of Preparative Inorganic Chemis-
try, New York: Academic, 1983, vol. 6.
7. Sheldrick, G.M., SHELXTL-97. Version 5.50, Madison
(WI, USA): Bruker AXS Inc., 1997.
8. Cordero, B., Gomez, V., Platero-Prats, A.E., et al., Dal-
ton Trans., 2008, p. 2832.
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