PHOSPHORUS, SULFUR, AND SILICON
5
∼
+
+
+
−1
6 12 2 2 6 12 2
348(12) [(C H NCS ) ] , 316(10) [C H NC) S] , 304(10)
1
42(100) [SCNC6H12] . IR (KBr, cm ):v2927 s (νas C–
+
+
[
C5H10TeS2C2N] , 200(22) [C5H10Te ], 175(18) [C6H13
H), 2852 m (νs C–H), 1635 m, 1484 s, 1447 m, 1410 s (νs
N–C=S), 1363 m (δ CH2), 1265 m, 1239 m, 1166 m, 1092 w
∼
−1
+
NCS2 ]. IR (KBr, cm ):v2927 s (νas C–H), 2852 m (νs C–
H), 1486 s, 1446 s (νs N–C=S), 1362 m (δ CH2), 1265 m,
and 945 m (νCS2), 1013 w, 974 w„ 899 w, 853 w, 796 w, 742 w,
1
1
190 m, 1096 w, 1044 w and 901 w (νCS2), 952 w, 854 w,
6
21 w, 449 w. H NMR (400 MHz, CDCl3, ppm): δ 4.01 (t,
1
3
7
67 w, 623 w, 451 w. H NMR (400 MHz, CDCl3, ppm): δ 4.02
JH–H = 6 Hz, 8H, CH2N), 3.16 (br s, 4H, CH2CH2Te), 2.66
3
(
t, JH–H = 6 Hz, 8H) CH2N, 3.26 (br s, 4H) (CH2)2CH2Te,
(
8
(
(
br s, 4H, CH2CH2Te), 1.78 (br s, 8H, CH2CH2N), 1.53 (sep,
H, CH2(CH2)2N). 13C NMR (100 MHz, CDCl3, ppm): δ 199.8
2
.16 (br s, 4H) CH2CH2CH2Te, 1.82 (br s, 8H) CH2CH2N, 1.76
br s, 2H) CH2(CH2)2Te, 1.56 (br s, 8H) CH2(CH2)2N. 13
NMR (100 MHz, CDCl3, ppm): δ 193.5 (CS2), 55.1 (CH2N),
(
C
CS2), 54.8 (CH2N), 40.8 (CH2Te), 33.1 (CH2CH2Te), 27.2
CH2CH2N), 26.8 (CH2(CH2)2N). Te NMR (128.18 MHz,
CDCl3, ppm): δ 771.1.
C8H8Te{S2CN(CH2)6}2](3). C8H8TeI2 (0.200 g, 0.411 mmol)
in chloroform (15 mL) was added slowly to (CH2)6NCS2Na
0.162 g, 0.823 mmol) in chloroform (15 mL). Yellow
125
3
1.1 ((CH2)2CH2Te), 27.2 (CH2CH2N), 26.9 (CH2(CH2)2N)
6.0 (CH2CH2CH2Te), 22.8 (CH2(CH2)2Te).
128.18 MHz, CDCl3, ppm): δ 503.2.
1
25
2
Te NMR
[
(
(
solid. M.p. 149–151°C. Yield 69% (0.164 g, 0.282 mmol).).
Anal. Calc. for C22H32N2S4Te: C, 45.53; H, 5.56; N, 4.82.
X-ray crystallography
+
Found: C, 46.07; H, 5.49; N, 4.98. FAB –MS (70 eV):
+
+
Data were collected on a Bruker APEX DUO diffractometer
equipped with an Apex II CCD detector at 100 K using omega
m/z 348(10) [(C6H12NCS2)2] , 316(5) [(C6H12NCS2)2S] ,
+
+
3
04(5) [C6H12NCS2Te] , 234(85) [C8H8Te ], 206(5)
TeS2C] , 175(10) [C6H12NCS2] , 142(90) [SCNC6H12] . IR
+
+
+
scans and integrated with SAINT. Multi-scan absorption cor-
[
(
∼
−1
rection (SADABS) was applied. The structures were solved
KBr, cm ):v2922 s (νs C–H), 2852 w (νas C–H), 1651 w,
by intrinsic phasing (SHELXT) and refined using full-matrix
1
1
569 w, 1483 s, 1429 s (νs N–C=S), 1382 w, 1356 w (δ CH2),
2
least-squares on F with SHELXL using the SHELXLE GUI.
263 m, 1195 m, 1157 m, 1091 w, 1050 w, 1003 w, and 945 m
1
Weighted R factors, Rw, and all goodness-of-fit indicators, are
(
νCS2), 972 w, 791 m, 731 w, 619 w, 562 w, 481 w, 423 w. H NMR
400 MHz, CDCl3, ppm): δ 7.15 (s, 4H, Ar-H), 4.43 (br s, 4H,
2
based on F . All nonhydrogen atoms were refined anisotropi-
(
cally. The hydrogen atoms of the C–H bonds were placed in ide-
alized positions and refined with Uiso tied to the parent atom.
The molecular graphics were prepared using GRETEP, POV-
RAY, and GIMP.35 CCDC-1487725 and 1487726 (5) contain the
supplementary crystallographic data for compounds 2 and 5,
respectively.
C6H4CH2Te), 3.98 (t, 8H, CH2N) 1.79 (br s, 8H, CH2CH2N),
.53 (br m, 8H, CH2(CH2)2N). 1 C NMR (100 MHz, CDCl3,
3
1
ꢀ
ꢀ
ppm): δ 200.0 (CS2), 140.3 (C3 –Ar) 130.3 (C5 –Ar) 127.5
ꢀ
(
2
C4 –Ar), 54.9 (s, CH2N), 44.5 (s, CH2Te), 27.2 (d, CH2CH2N),
6.9 (s, CH2(CH2)2N). 125Te NMR (128.18 MHz, CDCl3, ppm):
δ 608.9.
C4H8OTe{S2CN(CH2)6}2](4).
.552 mmol) in chloroform (15 mL) was added slowly
to (CH2)6NCS2Na (0.218 g, 1.104 mmol) in chloroform Conclusions
[
C4H8OTeI2
(0.250 g,
0
(
0
15 mL). Yellow solid. M.p. 145–149°C. Yield 33% (0.100 g,
In this paper, we report the synthesis of the first organohete-
rocyclic tellurium (IV) azepanedithiocarbamate complexes.
The obtained compounds are air stable solids, however, for
periods of more than 24 h they are unstable in solution. In
these compounds, the azepane-1-carbodithioate moiety shows
a great tendency to display disubstitution. The compounds were
characterized by conventional analytical techniques, including
.183 mmol).). Anal. Calc. for C18H32N2OS4Te: C, 39.43;
+
H, 5.88; N, 5.11. Found: C, 40.06; H, 6.09; N, 5.22. FAB –
+
MS (70 eV): m/z 142(100) [SCNC6H12] , 478(5) [M–
+
+
+
C4H8O] , 348(10) [(C6H12NCS2)2] , 316(10) [C14H24N2S3] ,
+
+
3
[
04(10) [TeS2CNC6H12] , 202(20) [C4H8OTe] 175(20)
∼
−1
+
C6H13NCS2] . IR (KBr, cm ):v2920 s (νas C–H), 2852 s (νs
C–H), 1653 m, 1473 m, 1444 s, 1418 s (νs N–C=S), 1385 s,
125
Te NMR, the results indicate that the ligand coordination
1
1
4
345 m, 1314 w (δ CH2), 1273 m, 1193 w, 1162 s, 1086 s,
is anisobidentate, observing the equivalence of the two ligand
units. Single-crystal X-ray diffraction was determined for two
of the complexes, where the tellurium atom displays a dis-
torted trigonalbipyramidal “sawhorse” geometry, with the lone
pair apparently stereochemically active, the tellurocycle sing
shows envelope and chair conformations for 2 and 5 while the
azepane-1-carbodithioate ring adopts a twisted chair conforma-
tion and the arrangement of the ligands prevents the generation
of intermolecular interactions.
006 m and 945 w (νCS2), 877 m, 821 w, 615 w, 550 w,
1
80 w. H NMR (400 MHz, CDCl3, ppm): δ 4.28 (br s, 4H,
3
OCH2CH2Te), 4.02 (t, JH–H = 6.00 Hz, 8H, CH2N), 3.10 (br
s, 4H, OCH2CH2Te), 1.82 (br s, 8H, CH2CH2N), 1.56 (br s,
8
H, CH2(CH2)2N). 13C NMR (100 MHz, CDCl3, ppm): δ 199.0
(
(
CS2), 66.7 (OCH2CH2Te), 54.9 (CH2N), 28.2 (CH2Te), 27.1
CH2CH2N), 26.8 (CH2(CH2)2N).
125
Te NMR (128.18 MHz,
CDCl3, ppm): δ 421.1.
C5H10Te{S2CN(CH2)6}2](5).
.5536 mmol) in chloroform (15 mL), was added slowly
to (CH2)6NCS2Na (0.219 g, 1.107 mmol) in chloroform
[
C5H10TeI2
(0.250
g,
0
Acknowledgments
The spectroscopic analyses (EI-MS and multinuclear 1H, 13C, and 125Te
NMR) were performed at the Centro de Investigaciones Químicas, UAEM.
(
15 mL). Yellow solid. M.p. 134–139°C. Yield 61% (0.185 g,
0
.339 mmol).). Anal. Calc. for C19H34N2S4Te: C, 41.77; H, 6.27;
+
N, 5.13. Found: C, 41.25; H, 6.38; N, 4.85. FAB –MS (70 eV):
m/z 142(100) [SCNC6H12] , 478(5) [(C16H12NCS2)2Te] , The authors are grateful to the staff for this service.
+
+