16
A. Gupta et al. / Journal of Organometallic Chemistry 894 (2019) 10e17
þ
(
126 MHz, CDCl
m/z ¼ 342.0495(observed), 342.0497 (calculated).
Synthesis of 6. Reagents used were 2-MeC
prepared by Br (1.05 mL, 6.58 mmol), 1,2-di-o-tolylditelluride
2.88 g, 6.58 mmol). A Yellowish liquid which solidified upon
3
):
d
(ppm) 633. ESI-MS (positive mode): [MþH]
(100 MHz, CDCl
130.76, 129.49, 128.92, 128.17, 63.38, 44.33, 18.50.
(126 MHz, CDCl ):
3
): d (ppm) 140.46, 138.29, 134.95, 131.53, 131.08,
125
Te NMR
þ
6
H
4
TeBr (in situ)
3
d
(ppm) 1223. ESI-MS (positive mode): [MþH]
2
m/z ¼ 358.0445 (observed), 358.0446 (calculated).
(
Synthesis of 11. The reagent used are 6 (0.5 g, 1.42 mmol) in CCl
4
1
cooling. yield: 0.80 g (45%). H NMR (400 MHz, CDCl
(
1
NMe
1
6
3
):
d
(ppm) 7.88
(10 mL), SO
NaOH aqueous solution (5 mL). Yield 0.39 g (76%), H NMR
(400 MHz, CDCl ): (ppm) 8.36 (d, 1H, AreH), 7.57 (t, 1H, AreH),
7.46 (t, 1H, AreH), 7.23e7.26 (m, 4H, AreH),7.12 (t, 1H, AreH), 3.51
(d,1H, Ar-CH ), 3.34 (d, 1H, Ar-CH ), 2.70 (s, 3H, Ar-CH ), 2.07 (s, 6H,
). C NMR (100 MHz, CDCl ): (ppm) 140.48, 139.86, 139.27,
133.75, 131.81, 131.46, 131.16, 130.80, 130.16, 128.94, 128.28, 127.46,
2 2 4
Cl (0.19 g, 1.42 mmol, 114 mL) in CCl (5 mL) and 2 M
1
d, 1H, AreH), 7.20 (s, 2H, AreH), 7.00e6.94 (m, 4H, AreH), 6.81 (t,
H, AreH), 3.43 (s, 2H, ArCH
2
), 2.37 (s, 2H, Ar-CH
3
), 2.17 (s, 6H,
3
d
13
2
). C NMR (100 MHz, CDCl ): (ppm) 144.59, 142.21, 141.07,
34.51, 129.09, 128.99, 128.81, 128.01, 126.60, 125.93, 124.13, 122.56,
3
d
2
2
3
125
13
6.55, 44.00, 27.22. TeNMR (126 MHz, CDCl
3
):
d
(ppm) 549. ESI-
NMe
2
3
d
MS (positive mode): [MþH]þ m/z ¼ 356.0654 (observed),
1
25
3
56.0653(calculated).
63.37, 44.45, 23.34. Te NMR (126 MHz, CDCl
3
):
d
(ppm) 1214. ESI-
þ
Synthesis of 7. Reagents used were 2,6-Me
2
C
6
H
3
TeBr (in situ)
(1.05 mL, 6.58 mmol) [1,2-bis(2,6-dimethylphenyl)
MS (positive mode): [MþH] m/z ¼ 372.0601 (observed), 372.0602
prepared by Br
2
(calculated).
ditelluride] (3.06 g, 6.58 mmol). White solid, yield: 0.78 g (44%);
Synthesis of 12. The reagent used are 7 (0.5 g,1.36 mmol) in CCl
(10 mL), SO Cl (0.18 g, 1.36 mmol, 110 L) in CCl (5 mL) and 2 M
NaOH aqueous solution (5 mL). Yield 0.43 g (82%), H NMR
(400 MHz, CDCl ): (ppm) 8.33 (d, 1H, AreH), 7.50 (t, 1H, AreH),
7.43 (td, 1H, AreH), 7.19 (d, 2H, AreH),7.01 (d, 2H, AreH), 3.33 (dd,
4
ꢁ
1
m.p. 88e90 C. H NMR (400 MHz, CDCl
AreH), 7.13e7.11 (m, 1H, AreH), 7.05 (d, 2H, AreH), 6.98 (t, 1H,
AreH), 6.85 (t, 1H, AreH), 6.61 (d, 1H, AreH), 3.42 (s, 2H, Ar-CH ),
):
(ppm) 143.82, 138.74, 135.95, 132.55, 129.74, 129.35, 129.13,
3
):
d
(ppm) 7.17e7.14 (m.1H,
2
2
m
4
1
2
3
d
13
2
.35 (s, 6H, CH
3
), 2.20 (s, 6H, NMe
2
)
C NMR (100 MHz, CDCl
3
13
d
2H, Ar-CH
(100 MHz, CDCl
130.80, 128.98, 128.94, 128.39, 63.55, 44.74, 22.99.
(126 MHz, CDCl ):
m/z ¼ 386.0758 (observed), 386.0759 (calculated).
Synthesis of 13. The reagent used are 8 (0.5 g, 1.18 mmol) in CCl
(10 mL), SO Cl (0.16 g, 1.18 mmol, 96 L) in CCl (5 mL) and 2 M
NaOH aqueous solution (5 mL). Yield 0.41 g (80%), H NMR
(400 MHz, CDCl ): (ppm) 7.82 (d, 1H, AreH), 7.32e7.37 (m, 3H,
AreH), 7.23 (d, 3H, AreH), 3.79 (d, 1H, Ar-CH ),3.60 (sept, 2H, Ar-
CH), 3.28 (d, 1H, Ar-CH ), 2.20 (s, 6H, NMe ), 1.23 (d, 6H, CH ),
). C NMR (100 MHz, CDCl ): (ppm) 154.50,
141.48, 138.40, 135.40, 132.55, 131.24, 130.67, 128.94, 128.55, 124.56,
2
), 2.42 (s, 6H, Ar-CH
3 2
), 2.08 (s, 6H, NMe ). C NMR
1
25
1
28.90,128.44,128.00,127.97,125.24, 64.67, 45.07, 24.49. Te NMR
3
): (ppm) 142.95, 140.75, 137.12, 133.72, 132.13,
d
þ
125
(
126 MHz, CDCl
3
):
d
(ppm) 410. ESI-MS (positive mode): [MþH] m/
Te NMR
þ
z ¼ 370.0811 (observed), 370.0810(calculated).
3
d
(ppm) 1240. ESI-MS (positive mode): [MþH]
i
Synthesis of 8. Reagents used were 2,6- Pr
2
C
6
H
3
TeBr (in situ)
prepared
by
Br
2
(1.05 mL,
6.58 mmol)
[1,2-bis(2,6-
4
diisopropylphenyl)ditelluride] (3.80 g, 6.58 mmol), provided
a
2
2
m
4
ꢁ
1
1
white solid. Yield 0.76 mg (43%), m.p. 95e97 C. H NMR (400 MHz,
CDCl ): (ppm) 7.28 (t, 1H, AreH), 7.14 (t, 2H, AreH), 7.01 (d, 1H,
AreH), 6.94 (t, 1H, AreH), 6.83 (d, 1H, AreH) 6.77e6.73 (m, 1H,
AreH), 3.69 (sept, 2H, Ar-CH), 3.46 (s, 2H, Ar-CH ), 2.21 (s, 6H,
),1.05 (d,12H, iso-propyl). C NMR (100 MHz, CDCl ): (ppm)
55.53, 140.91, 134.67, 129.77, 128.73, 128.68, 127.84, 125.60, 123.93,
3
d
3
d
2
2
2
2
3
13
13
NMe
2
3
d
0.98 (d, 6H, CH
3
3
d
1
125
125
122.93, 66.84, 44.20, 39.51, 24.83.
Te NMR (126 MHz, CDCl
3
):
63.04, 44.54, 32.75, 24.95, 24.81.
d
Te NMR (126 MHz, CDCl
3
):
þ
þ
d
(ppm) 350. ESI-MS (positive mode): [MþH] m/z ¼ 426.1436
(ppm) 1256. ESI-MS (positive mode): [MþH] m/z ¼ 442.1388
(
observed), 426.1436 (calculated).
(observed), 442.1385 (calculated).
Synthesis of 14a·14b. The reagents used are 9 [37] (0.75 g,
1.46 mmol) in CCl (10 mL), SO Cl (0.2 g, 1.47 mmol, 119 L) in CCl
(5 mL) and 2 M NaOH aqueous solution (5 mL). H NMR (400 MHz,
CDCl ): 8.1e8.0 (v br), 7.6e7.2 (v br), 4.8 (dd, br), 4.3 (dd, br),
3.6e3.1 (br), 3.0e2.8 (br), 2.4e2.0 (v br), 1.8e1.6 (v br),
(126 MHz, CDCl ):
5.3. General procedure for the oxidation of tellurides 10e14 by
4
2
2
m
4
1
halogenation followed by hydrolysis
3
125
A solution of tellurides 5e9 in CCl
4
(15 mL) was chlorinated by
Te NMR
ꢁ
þ
gradual addition of SO
2
Cl
2
in CCl
4
solution (10 mL) at 0 C under
3
d
(ppm) 1119. ESI-MS (positive mode): [MþH]
inert atmosphere and the solution was stirred for an additional
0 min and was then permitted to stir at room temperature for
m/z ¼ 529.2183 (observed), 529.2182 (calculated).
3
Synthesis of 14c. The reagents used are 9 [37] (0.75 g,
additional 3 h. The precipitate formed was filtered and washed with
hexane (2x10 mL). The resulting solid was dried under vacuum to
afford white solids of the corresponding diorganyltellurium(IV)
chlorides and was used as such for the next step without any
further purification. A suspension of the chlorinated compound in
1.46 mmol) in CCl
4 2 2 4
(10 mL), SO Cl (0.2 g, 1.47 mmol, 119 mL) in CCl
(5 mL) and 2 M NaOH aqueous solution (5 mL). Yield 0.65 g (76.2%),
ꢁ
1
m.p. 194 C. H NMR (500 MHz, CDCl
8.05 (d, 1H, AreH), 7.49 (s, br, 1H, AreH), 7.38 (s, br, 1H, AreH), 7.33
(s, br, 1H, AreH), 7.21 (d, br, 1H, AreH), 4.64 (dd, 1H, Ar-CH ), 4.13
(dd, 1H, Ar-CH ), 3.38 (t, 1H, Ar-CH ), 3.29 (d, 2H, Ar-CH ), 3.20 (d,
1H, Ar-CH ), 2.99 (d, 1H, Ar-CH ), 2.79 (d, 1H, Ar-CH ), 2.28 (s, br,
8H, CH ), 2.09 (s, br, 4H, CH ), 1.75 (s, br, 12H, CH
(126 MHz, CDCl ):
3
) d (ppm) 8.11 (d, 1H, AreH),
2
2
M NaOH (10 mL) was refluxed for 3 h. A few drops of ethanol were
2
2
2
added until the product had entirely dissolved and the solution was
filtered in hot condition. The organic component was extracted
2
2
2
125
3
3
3
),
Te NMR
þ
with CH
anhydrous Na
2
Cl
2
and the combined organic layer was dried over
SO and concentrated by rotary evaporator to afford
3
d
(ppm) 1120, ESI-MS (positive mode): [M] m/
2
4
z ¼ 529.2188 (observed), 529.2182 (calculated). Elemental analysis:
white solids. The white solids were washed with hexane (2x10 mL)
to give the pure product in ~80% yield. Single crystals of 10 and 14
suitable for single-crystal diffraction analysis were obtained by
Anal. Calcd. for C24 39ClN OTe: C, 51.23; H, 6.99; N, 9.96. Found: C,
H
4
ꢀ
1
51.1879; H, 6.3321; N, 8.8794. FTIR: ῡ (OH) 3417 cm
.
slow diffusion of hexane in CH
compounds at room temperature
2
Cl
2
solution of the respective
6. X-ray crystallographic study
Synthesis of 10. The reagents used are 5 (0.5 g, 1.47 mmol) in
CCl (10 mL), SO Cl (0.2 g,1.47 mmol,119 L) in CCl (5 mL) and 2 M
NaOH aqueous solution (5 mL). Yield 0.41 g (79%), H NMR
400 MHz, CDCl ): (ppm) 8.42 (d, 1H, AreH), 7.56 (d, 3H, AreH),
.46 (t, 1H, AreH), 7.36 (d, 3H, AreH),7.18 (d, 1H, AreH), 3.56 (d, 1H,
The single crystal X-ray diffraction measurements were per-
formed on a Rigaku Saturn 724 diffractometer and an Oxford
Diffraction Gemini diffractometer. The data were corrected for
Lorentz, polarization, and absorption effects. The structures were
determined by routine direct methods using SHELXT [43] and
Fourier methods and refined by full-matrix least squares with the
4
2
2
m
4
1
(
7
3
d
13
2 2 2
Ar-CH ), 3.25 (d, 1H, Ar-CH ), 2.06 (s, 6H, NMe ). C NMR