Iron-catalyzed formation of C-Se and C-Te bonds through cross coupling of aryl halides with Se(0) and Te(0)/nano-Fe3O4@GO

Article abstract of DOI:10.1055/s-0033-1338488

The formation of C-Se and C-Te bonds is of synthetic and biological importance. Graphene oxide based nano-Fe₃O₄ (nano-Fe ₃O₄@GO) is used as a reusable catalyst for the efficient synthesis of diselenides and ditellurides, through cross coupling of Se(0) or Te(0) with aryl iodides. The magnetic heterogeneous catalyst could be easily recovered and reused many times without significant loss of catalytic activity. In addition the superiority of nano-Fe₃O₄@GO over pristine nano-Fe₃O₄ is established. Georg Thieme Verlag Stuttgart. New York.

Full text of DOI:10.1055/s-0033-1338488

PAPER
▌2337
paper
Iron-Catalyzed Formation of C–Se and C–Te Bonds through Cross Coupling
of Aryl Halides with Se(0) and Te(0)/Nano-Fe3O4@GO
Iron-Catalyzed Formation of C–Se and C–Te Bonds
Mohammad Zaman Kassaee,*a Elaheh Motamedi,a Barahman Movassagh,b Samira Poursadeghia
a
Department of Chemistry, Tarbiat Modares University, P.O. Box 14155-175, Tehran, Iran
Fax +98(21)88006544; E-mail: Kassaeem@Modares.ac.ir
b
Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran
Received: 25.12.2012; Accepted after revision: 09.05.2013
teresting properties.24 Layering magnetite nanoparticles
Abstract: The formation of C–Se and C–Te bonds is of synthetic
on the surface of graphene oxide results in nanocompos-
and biological importance. Graphene oxide based nano-Fe3O4
ites that can be tailored with different desirable functional
properties such as biocompatibility, electrical conductivi-
(nano-Fe3O4@GO) is used as a reusable catalyst for the efficient
synthesis of diselenides and ditellurides, through cross coupling of
Se(0) or Te(0) with aryl iodides. The magnetic heterogeneous cata- ty, or chemical and physical stability that are necessary for
particular applications.25
lyst could be easily recovered and reused many times without sig-
nificant loss of catalytic activity. In addition the superiority of nano-
Fe3O4@GO over pristine nano-Fe3O4 is established.
Over the last few decades, organodichalcogens, the sele-
nium or tellurium counterparts of organic peroxides, have
played an important role in organic chemistry as interme-
Key words: graphene oxide, cross coupling, recyclability, nano-
Fe3O4 catalyst, diselenide, ditelluride
diates because of their stability, ease of handling, and re-
activity.26,27 Traditional methods for the formation of
diselenides include oxidation of selenols,28 reaction of so-
Graphene (G) has a monolayer arrangement of carbon at-
oms in a honeycomb network; graphene has attracted
dium or lithium diselenides with alkyl halides,29 reaction
of selenourea with alkyl halides,30 reduction of selenocy-
enormous scientific activity due to its excellent electrical,
anates.31 Aluminum-induced, copper-catalyzed coupling
1–5
thermal, and mechanical properties.
Graphene-based
of aryl iodides with selenium afforded the corresponding
diaryl selenides.32,33 Correspondingly, Kumar et al. re-
ported a copper-catalyzed/mediated Se–N coupling reac-
tion for the synthesis of isoselenazolones.34 In addition,
various metal-based catalysts in combination with differ-
ent ligands are generally employed for synthesis of sele-
nides by cross coupling of their halides, but most of these
synthetic approaches involve specially designed ligands
or well-defined catalyst/reagent(s); this may increase the
cost and limit the scope of their applications.35
composites are emerging as a new class of materials; they
have created the opportunity for the novel use of two-
dimensional carbon as a superior platform for metal
nanoparticles (platinum, palladium, gold, copper) and
metal oxides (titanium dioxide, clay, silica, cobalt oxide,
zinc oxide).6–12 One of the most important derivatives of
graphene is graphene oxide (GO), which is a layered com-
pound with oxygen functional groups that can be used as
anchoring sites for metal nanoparticles to produce gra-
phene nanoparticle hybrids.13 In particular, the combina-
tion of graphene and functional nanoparticles may lead to
nanocomposites of graphene bearing with metals or inor-
ganic metal oxides or sulfides with interesting properties
for many potential applications including chemical sen-
sors, energy storages, catalyses, hydrogen storages, super-
capacitors, lithium ion batteries, etc.14–16 Fabrication of
these functional nanocomposites via a controllable, cost-
effective, and fast approach has likewise aroused interest
among researchers.17 In recent years, composite systems
containing magnetic nanoparticles have become the sub-
ject of intensive research, because of their potential inte-
gration in a broad range of technological applications such
as magnetic fluids,18 data storage,19 biotechnology/bio-
medicine,20 catalysis,21 magnetic resonance imaging,22
environmental remediation,23 etc. Nanocomposites of
magnetite Fe3O4 nanoparticles (NPs), due to the presence
of iron ions in two valence states Fe2+ and Fe3+, have in-
Novel catalytic procedures, especially in the absence of a
ligand, are required for the efficient synthesis of disele-
nides. Heterogeneous nanocatalysts offer higher surface
area and low-coordinated sites that are responsible for the
higher catalytic activity.36 Organic reactions catalyzed by
metallic nanoparticles are currently an area of intensive
research because they afford a more effective process and
allow improvement in relation to traditional methodolo-
gies. Recently, Braga et al. reported a one-pot synthesis of
symmetrical diselenides and ditellurides from halides
with CuO NPs/Se(0) as well as Te(0)/KOH, but they did
not survey the recovery and reusability of this catalyst.37
Iron has been investigated as a catalyst in the formation of
carbon–carbon and carbon–heteroatom bonds due to its
low cost, nontoxicity, and ease of application. Iron–cata-
lyzed cross-coupling reactions of aryl halides with nitro-
gen, oxygen, and sulfur nucleophiles resulted in the
formation of C–N, C–O, and C–S bonds, respectively.38–42
Finally, as part of our ongoing research on the synthesis
and applications of graphene nanocomposites,43 herein we
disclose an efficient method for the preparation of sym-
metrical diaryl diselenides and ditellurides over graphene
SYNTHESIS 2013, 45, 2337–2342
Advanced online publication: 27.06.2013
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DOI: 10.1055/s-0033-1338488; Art ID: SS-2013-N0996-OP
© Georg Thieme Verlag Stuttgart · New York

2338
M. Z. Kassaee et al.
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oxide supported nano-Fe3O4 catalyst (nano-Fe3O4@GO). XRD of the synthesized nano-Fe3O4@GO is comparable
To the best of our knowledge, this is the first report of to that of pristine nano-Fe3O4 indexing to (220), (311),
C–Se and C–Te bond formation via iron–catalyzed cross– (400), (422), (511), and (440) planes of a cubic unit cell of
coupling of Se(0) or Te(0) with aryl iodides to give sym- magnetite, and appearing at 30.07°, 35.53°, 43.41°,
metrical diorgano dichalcoganides. Also, the catalytic ac- 53.51°, 57.19°, and 62.73°, respectively (Supporting In-
tivity of nano-Fe3O4@GO is compared and contrasted to formation, Figure S2). The structural properties of nano-
that of pristine Fe3O4 NPs demonstrating the significance Fe3O4, even after their loading on the surface of graphene
of catalyst design. While both catalysts enjoy rather easier oxide, are not changed and the nanocomposite retains its
workups, nano-Fe3O4@GO affords higher yields with crystallinity. TEM of pristine nano-Fe3O4 shows agglom-
shorter reaction times (Figure 1).
eration of nanoparticles induced by their inherent magne-
tism. These magnetic forces are overcome by grafting the
nanoparticles onto the surface of graphene oxide, making
the TEM of our hybrid sample show nearly spherical
nano-Fe3O4 that are homogeneously distributed over the
graphene oxide sheets (Figure 2). Hence, better dispersion
of nano-Fe3O4 on graphene oxide improves the catalytic
activity of nano-Fe3O4@GO.
Figure 1
We find a conspicuous superiority of nano-Fe3O4@GO
over pristine Fe3O4 nanoparticles through their catalytic
synthesis of diselenides and ditellurides; higher yields and
considerably shorter reaction times were encountered us-
ing nano-Fe3O4@GO (Figure 1, Table 1). Such catalytic
activities appear to be related to the microstructures, dis-
persity, morphology, and magnetic properties of pristine
and graphene oxide supported Fe3O4 nanoparticles, as in-
dicated by FT-IR, X-ray diffraction (XRD), transmission
electron spectroscopy (TEM), and vibrating sample mag-
netometer (VSM) analyses.
Figure 2 TEM images of (a) nano-Fe3O4 and (b) nano-Fe3O4@GO
hybrid nanoparticles.
More specifically, the magnetization value of nano-Fe3O4
and nano-Fe3O4@GO are 60.0 and 21.0 emu/g at 25 °C,
respectively (Figure 3). Evidently, the smaller magnetiza-
tion of our nanohybrid catalyst than pristine Fe3O4
nanoparticles is due to the dispersion of the Fe3O4
nanoparticles on the surface of graphene oxide.
The infra red spectra of the synthesized graphene oxide,
nano-Fe3O4, and nano-Fe3O4@GO appear consistent
with their structures (see the Supporting Information,
Figure S1). In the graphene oxide spectrum, the peak at
1731 cm–1 corresponds to the stretching band of C=O in
carboxylic acid or carbonyl moieties. The intense bands at
3432 and 1253 cm–1 are attributed to stretching and bend-
ing, respectively, of O–H. The peak at 1620 cm–1 (aromat-
ic C=C) could be assigned to the skeletal vibrations of un-
oxidized graphitic domains of graphene oxide.44 In the in-
frared spectrum of pristine nano-Fe3O4, we encountered a
peak at 584 cm–1 for the Fe–O vibration, while the absorp-
tion at 3440 cm–1 is attributed to the O–H stretching vibra-
tions of the adsorbed moisture on the surface of nano-
Fe3O4.45 The FT-IR spectrum of nano-Fe3O4@GO shows
both the Fe–O (around 578 cm–1) and graphene absorp-
tions, confirming the existence of Fe3O4 in this nanohy-
brid, yet this spectrum differs from those of graphene
oxide and pristine nano-Fe3O4 by the anticipated broaden-
ing and weakening of the composite absorptions, indicat-
ing that nano-Fe3O4 is coordinated to graphene oxide.46
Figure 3 Magnetization curves for pristine nano-Fe3O4 and nano-
Fe3O4@GO hybrid
In the first set of experiments, the activity of our synthe-
sized nanocatalysts was compared and contrasted under
the same reaction conditions, employing iodobenzene
(1a) as a representative halide, elemental selenium (2.0
Synthesis 2013, 45, 2337–2342
© Georg Thieme Verlag Stuttgart · New York

PAPER
Iron-Catalyzed Formation of C–Se and C–Te Bonds
2339
equiv), and KOH (2.0 equiv) in dimethyl sulfoxide (2.0 In addition, we have shown the impact of the amount of
mL), monitoring formation of the corresponding diphenyl catalyst (nano-Fe3O4@GO) (Table 2, entries 1–5) and dif-
diselenide (2a) (Table 1). Our results indicate that nano- ferent solvents (entries 6–9) on the product yield. No
Fe3O4@GO (7 mol%) gives diphenyl diselenide in 50% product is observed in the absence of the catalyst (entry
yield after two hours, and the reaction is complete after 1). When the amount of nano-Fe3O4@GO is increased
four hours (98%), and extending the reaction time to 24 from 1.5 to 7 mol%, the yield of diphenyl diselenide (2a)
hours has no influence on the product yield. In contrast, rises from 75% to 98% (entries 2–4). Increasing the
pristine nano-Fe3O4 (10 mol%) gives no product after four amount of catalyst to 15 mol% does not show a significant
hours, but after eight hours diphenyl diselenide (2a) is influence, affording the desired product with the same
produced in 40%, and a maximum yield of 63% is ob- yield (98%, entry 5). The desired product is not obtained
tained after 24 hours. Similar results are obtained with re- in toluene or tetrahydrofuran (entries 8 and 9). However,
placing Se with Te, where nano-Fe3O4@GO (7 mol%) the reaction is highly facilitated by polar aprotic solvents
gives diphenyl ditelluride in 96% yield after four hours, among them, dimethyl sulfoxide is the most efficient sol-
but in the presence of pristine nano-Fe3O4 (10 mol%), di- vent for this reaction affording the best yield for prepara-
phenyl ditelluride is obtained in a maximum yield of 60% tion of diphenyl diselenide (2a) (entry 4). These results
after 24 hours.
are consistent with a previous report34 and suggest that the
success of the reaction depends on the polarity of the sol-
vent.
Table 1 Optimization of Time and Comparison between Catalytic
Activities of Prepared Nanocatalysts
In order to explore the scope and limitations of this meth-
odology, a series of aryl and heteroaryl halides 1 were ex-
amined in the synthesis of symmetrical diselenides 2a–i
and ditellurides 3a–h, under standard conditions (Table 3).
DMSO, KOH, 90 °C
Se0
+
Ph–I
Ph–Se–Se–Ph
1a
2a
Entry
Time (h)
Yielda (%)
Table 3 Synthesis of Diselenides and Ditellurides via a One-Pot
Coupling Reaction Procedure
Nano-Fe3O4@GO
(7 mol%)
Nano-Fe3O4
(10 mol%)
DMSO, KOH, 4 h, 90 °C
E0
+
R–X
R–E–E–R
1
2
3
4
5
6
1
–
–
Nano-Fe3O4@GO (7 mol%)
2 E = Se
3 E = Te
1
2
50
84
98
98
98
–
Entry
1
R
X
E
Product Yielda
3
–
(%)
4
–
2a
2a
2a
Ph
IBrCl
Se
98
73
60
8
40
63
24
a Isolated yield.
2
3
4-MeC6H4
4-MeOC6H4
3-MeOC6H4
4-O2NC6H4
4-ClC6H4
4-BrC6H4
4-HOCC6H4
2-thienyl
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Se
Se
Se
Se
Se
Se
Se
Se
Te
Te
Te
Te
Te
Te
Te
Te
2b
2c
2d
2e
2f
95
98
85
96
78
84
93
90
96
96
98
95
75
78
95
87
Table 2 Optimization of Solvent and Catalyst Amount
4
KOH, 4 h, 90 °C
5
Se0
+
Ph–I
Ph–Se–Se–Ph
1a
2a
6
Entry
Solvent
Nano-Fe3O4@GO Yielda
(mol%)
7
2g
2h
2i
(%)
8
1
2
3
4
5
6
7
8
9
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
0.0
1.5
3.5
7
–
9
75
92
98
98
87
81
–
10
11
12
13
14
15
16
17
Ph
3a
3b
3c
3d
3e
3f
4-MeC6H4
4-MeOC6H4
4-O2NC6H4
4-ClC6H4
4-BrC6H4
4-HOCC6H4
2-thienyl
15
7
MeCN
toluene
THF
7
7
3g
3h
7
–
a Isolated yield.
© Georg Thieme Verlag Stuttgart · New York
a Isolated yield.
Synthesis 2013, 45, 2337–2342

2340
M. Z. Kassaee et al.
PAPER
tometer (VSM) with a maximum applied magnetic field of 6 kOe.
The hysteresis of the magnetization was obtained by varying H be-
tween +8000 and –8000 Oe at 300 K. The 1H and 13C spectra were
measured at 500.1, and 125.7 MHz, respectively, on a Bruker DRX
500-Avance FT-NMR instrument with CDCl3 as the solvent. Mass
spectra were recorded on Agilent Model: Agilent 5975 instrument.
Elemental analyses were performed using Perkin Elmer 2400 Series
Elemental Analyzer.
As anticipated, iodides are more reactive than bromides
and chlorides. In addition, both electron-rich and electron-
deficient aryl iodides are effective in the synthesis of the
corresponding products in good to excellent yields. An
improvement associated with this methodology is that a
wide range of functional groups are tolerated in this pro-
cess, including: methyl, methoxy, aldehyde, nitro, bromo,
and heteroaryl moieties. These results allow for the explo-
ration of the regioselectivity of the reaction, with the prep-
aration of selective bromo and chloro dichalcogenides
(Table 3, entries 6, 7, 15, and 16).
Nano-Fe3O4@GO
Nano-Fe3O4@GO was synthesized via a previously reported two-
step method.43 Graphene oxide (GO) was prepared from purified
natural graphite using modified Hummer’s method where graphite
was treated with H2SO4 and KMnO4.47 Then uniform coatings of
Fe3O4 NPs on GO were obtained by co-precipitation of FeCl3·6 H2O
and FeCl2·4 H2O (2:1 molar ratio), in the presence of GO, giving
nano-Fe3O4@GO. Specifically, GO (40 mg) in H2O (40 mL) was
sonicated for 30 min, to which a soln of FeCl3 (800 mg) and FeCl2
(300 mg) in deionized H2O (50 mL) was added at r.t. The soln tem-
perature was raised to 85 °C. At this point, the pH was increased to
10 by addition of 30% NH3 soln. After stirring rapidly for 45 min,
the resulting black precipitate was centrifuged at 4000 rpm for 15
min and washed with deionized H2O (3 ×) and finally dried at 60 °C,
where a uniform thin leaf formed over the watch glass. For compar-
ison, unsupported Fe3O4 NPs were prepared using the same proce-
dure in the absence of GO.
Finally, the catalytic activity and the ability to recycle and
reuse our nano-Fe3O4@GO were studied. The catalyst
was separated by an external magnet and it was reused in
subsequent experiments under similar reaction condi-
tions. Yields of the product decreased only slightly after
four trials (Table 4).
Table 4 Reusability of Nano-Fe3O4@GO Catalyst
Run
Yield (%)
Recovery of nano-Fe3O4@GO
1
2
3
4
98
98
95
91
99
99
99
99
Diselenides 2 and Ditellurides 3; General Procedure
Se(0) (1.0 mmol) in anhyd DMSO (2.0 mL) and KOH (2.0 equiv)
was added to a stirred soln of aryl halide (1.0 mmol) and nano-
Fe3O4@GO (or Fe3O4 NPs), at 90 °C (TLC monitoring). When the
reaction was complete, the contents of the flask were allowed to
cool, and EtOAc–H2O (1:1) were added and the organic layer was
washed and separated. The aqueous layer was further washed with
a further portion of EtOAc (10 mL), and the combined organic ex-
tracts were dried (anhyd MgSO4). The solvent and volatiles were
completely removed under vacuum to give the crude product, which
was subjected to column chromatography rendering diaryl disele-
nides. 1H and 13C NMR spectra of different diselenides appeared are
given that are consistent with those of the authentic samples.
Ditellurides were synthesized analogously starting from Te(0).
In conclusion, an interesting methodology has been devel-
oped for synthesis of synthetically and biologically im-
portant dichalcogenides in
a recyclable, catalytic
protocol. For the first time, pristine nano-Fe3O4, and gra-
phene oxide based nano-Fe3O4 (nano-Fe3O4@GO) are
employed as magnetic heterogeneous catalysts, in synthe-
ses of diselenides and ditellurides, using elemental Se(0)
or Te(0) and aryl iodides. Although diaryl monoselenides
and monotellurides are often formed in such coupling re-
actions in the presence of a copper catalyst,32,33,36 surpris-
ingly our catalyst synthesized diaryl diselenides and
ditellurides as the sole product of this reaction. While both
catalysts enjoy rather easier workups, nano-Fe3O4@GO
affords higher yields with shorter reaction times.
Diphenyl Diselenide (2a)37
Orange solid; yield: 154 mg (98%); mp 58–60 °C.
IR (KBr): 3049, 1562, 1448, 723 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.29–7.21 (m, 3 H), 7.60–7.56 (m,
2 H).
13C NMR (125 MHz, CDCl3): δ = 127.7, 129.3, 131.6, 133.0.
Di-p-tolyl Diselenide (2b)37
Pale yellow oil; yield: 162 mg (95%).
IR (KBr): 2923, 1624, 1391, 792 cm–1.
1H NMR (500 MHz, CDCl3): δ = 2.34 (s, 3 H), 7.09 (d, J = 8.4 Hz,
2 H), 7.50 (d, J = 8.4 Hz, 2 H).
Natural flake graphite was provided by Qingdao Dingding Graphite
Products Factory. FeCl3·6 H2O, and FeCl2·4 H2O (Aldrich, 98%),
deionized H2O, and NH4OH (Merck, 25%) were employed to pro-
duce Fe3O4 nanoparticles (NPs). KMnO4, H2SO4 (98%), and H2O2
(30%) were purchased from Aldrich Co. Other reagents and sol-
vents used in this work were obtained from Fluka or Merck and they
were used without further purification.
13C NMR (125 MHz, CDCl3): δ = 22.7, 127.7, 130.9, 133.4, 138.0.
Bis(4-methoxyphenyl) Diselenide (2c)37
Yellow solid; yield: 183 mg (98%); mp 135–137 °C.
IR (KBr): 2930, 1586, 1289, 818 cm–1.
1H NMR (500 MHz, CDCl3): δ = 3.82 (s, 3 H), 6.76 (d, J = 8.7 Hz,
2 H), 7.53 (d, J = 8.7 Hz, 2 H).
FT-IR spectra were recorded using KBr pellets with a Thermo
Spectrometer. Samples were characterized by X-ray diffraction
(XRD; Philips Xpert MPD, Cu Kα irradiation, λ = 1.5418 Å). In ad-
dition, transmission electron microscopy (TEM; Philips, EM208S,
Netherlands, at 100 kV of acceleration voltage) was employed to
observe the morphology of nano-Fe3O4@GO hybrids and Fe3O4
NPs. The magnetic properties of nano-Fe3O4@GO nanocomposite
and magnetite nanoparticles were compared as a function of the ap-
plied magnetic field H using a LDJ 9600 Vibrating Sample Magne-
13C NMR (125 MHz, CDCl3): δ = 55.3, 114.9, 122.3, 136.1, 160.3.
Bis(3-methoxyphenyl) Diselenide (2d)37
Pale yellow oil; yield: 159 mg (85%).
IR (KBr): 2927, 1581, 1280, 912 cm–1.
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Iron-Catalyzed Formation of C–Se and C–Te Bonds
2341
1H NMR (500 MHz, CDCl3): δ = 3.78 (s, 3 H), 6.79–6.76 (m, 1 H),
7.26–7.16 (m, 3 H).
1H NMR (500 MHz, CDCl3): δ = 3.72 (s, 3 H), 6.80 (d, J = 8.8 Hz,
2 H), 7.71 (d, J = 8.8 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 55.3, 113.9, 116.7, 123.5, 129.8,
13C NMR (125 MHz, CDCl3): δ = 55.2, 111.4, 127.4, 135.2, 161.3.
130.9, 159.9.
Bis(4-nitrophenyl) Ditelluride (3d)37
Bis(4-nitrophenyl) Diselenide (2e)37
Brownish-orange solid; yield: 194 mg (96%); mp 124–126 °C.
IR (KBr): 3079, 1503, 1334, 837 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.64 (d, J = 8.6 Hz, 2 H), 8.19 (d,
J = 8.6 Hz, 2 H).
Brownish-orange oil; yield: 240 mg (95%).
IR (KBr): 3023, 1511, 1321, 817 cm–1.
1H NMR (500 MHz, CDCl3): δ = 8.41 (d, J = 8.7 Hz, 2 H), 8.85 (d,
J = 8.7 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 114.8, 124.6, 131.8, 153.3.
13C NMR (125 MHz, CDCl3): δ = 124.3, 130.5, 138.9, 147.6.
Bis(4-chlorophenyl) Ditelluride (3e)37
Dark orange oil; yield: 180 mg (75%).
IR (KBr): 3075, 1466, 1008, 721 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.17 (d, J = 8.4 Hz, 2 H), 7.60 (d,
J = 8.4 Hz, 2 H).
Bis(4-chlorophenyl) Diselenide (2f)37
Orange oil; yield: 149 mg (78%).
IR (KBr): 3070, 1451, 1013, 821 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.25 (d, J = 8.4 Hz, 2 H), 7.50 (d,
J = 8.4 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 112.1, 129.9, 134.7, 139.4.
13C NMR (125 MHz, CDCl3): δ = 128.8, 129.4, 133.3, 134.3.
Bis(4-bromophenyl) Ditelluride (3f)37
Dark orange oil; yield: 222 mg (78%).
IR (KBr): 3043, 1464, 1020, 791 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.53 (d, J = 8.3 Hz, 2 H), 7.53 (d,
J = 8.3 Hz, 2 H).
Bis(4-bromophenyl) Diselenide (2g)37
Dark orange oil; yield: 197 mg (84%).
IR (KBr): 3037, 1473, 1004, 817 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.59–7.40 (m, 4 H).
13C NMR (125 MHz, CDCl3): δ = 122.4, 132.3, 133.4, 134.6.
13C NMR (125 MHz, CDCl3): δ = 112.7, 122.9, 132.8, 139.6.
4,4′-Diselanediyldibenzaldehyde (2h)37
Brown oil; yield: 172 mg (93%).
4,4′-Ditellanediyldibenzaldehyde (3g)37
Dark brown oil; yield: 223 mg (95%).
IR (KBr): 3479, 1656, 1134, 837 cm–1.
IR (KBr): 3454, 1663, 1113, 816 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.33 (d, J = 8.4 Hz, 2 H), 7.54 (d,
J = 8.4 Hz, 2 H), 9.75 (s, 1 H).
1H NMR (500 MHz, CDCl3): δ = 7.61 (d, J = 8.4 Hz, 2 H), 7.84 (d,
J = 8.4 Hz, 2 H), 9.81 (s, 1 H).
13C NMR (125 MHz, CDCl3): δ = 124.4, 126.5, 132.0, 136.7, 191.1.
13C NMR (125 MHz, CDCl3): δ = 119.4, 129.8, 131.1, 138.2.
Dithiophen-2-yl Diselenide (2i)
Dark orange oil; yield: 147 mg (90%).
Dithiophen-2-yl Ditelluride (3h)
Dark orange oil; yield: 185 mg (87%).
IR (KBr): 3479, 1533, 1104, 771 cm–1.
IR (KBr): 3423, 1503, 1085, 737 cm–1.
1H NMR (500 MHz, CDCl3): δ = 6.87 (m, 1 H), 7.09 (m, 1 H), 7.31
(m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 128.0, 131.4, 134.7, 135.3.
1H NMR (500 MHz, CDCl3): δ = 6.94 (m, 1 H), 7.46–7.42 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 114.4, 128.8, 130.9, 133.9.
MS: m/z (%) = 57 (60), 82 (100), 119 (51), 149 (62), 166 (98), 197
MS: m/z (%) = 57 (20), 69 (29), 82 (30), 91 (100), 165 (23), 211 (9),
(32), 245 (97), 408 (29), 426 (M+, 2).
245 (30), 279 (7), 326 (M+, 18).
Anal. Calcd for C8H6S2Te2: C, 22.80; H, 1.43. Found: C, 22.96; H,
1.52.
Anal. Calcd for C8H6S2Se2: C, 29.64; H, 1.87. Found: C, 29.93; H,
1.91.
Diphenyl Ditelluride (3a)37
Supporting Information for this article is available online at
Yellow oil; yield: 199 mg (96%).
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
m
tgioSrantnugIifoop
r
itmnatr
IR (KBr): 3055, 1569, 1467, 732 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.24–7.20 (m, 3 H), 7.75–7.69 (m,
2 H).
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