Hexavalent Organotellurium Compounds
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(decomp); H NMR (CDCl3, 258C, CHCl3): d=2.58 (s, 3H), 7.56 ppm (s,
7.24 (t, 3J(H,H)=7 Hz, 8H), 7.14 7.20 (m, 4H), 7.08 (t, 3J(H,H)=7 Hz,
2H), 3.76 ppm (s, 2H); 13C NMR (CDCl3, 258C, CHCl3): d=151.9 (s),
148.1 (s), 140.1 (s), 135.0 (d), 134.4 (d), 133.1 (d), 131.7 (d), 130.5 (d),
128.4 (d), 127.8 (d), 125.0 (d), 122.2 (d), 46.5 ppm (s); 125Te NMR
(CDCl3, 258C, (CH3)2Te): d=403.7 ppm; elemental analysis calcd (%)
for C37H32STe: C 69.84, H 5.06; found: C 70.14, H 5.00.
16H); 19F NMR (CDCl3, 258C, CFCl3): d=À63.2 ppm (s, 12F); 13C NMR
(CDCl3, 258C, CHCl3): d=19.8 (q, 1J(C,Te)=86 Hz), 123.6 (q, 1J(C,F)=
273 Hz), 125.2 (d), 131.9 (q, 2J(C,F)=33 Hz), 132.2 (d), 158.8 ppm (s,
1J(C,Te)=57 Hz); 125Te NMR (CDCl3, 258C, (CH3)2Te): d=409 ppm; ele-
mental analysis calcd (%) for C29H19ClF12Te: C 45.92, H 2.52; found: C
45.72, H 2.35.
Ph5(nBu)Te (13): Colorless crystals; m.p. 130 1318C; 1H NMR (CDCl3,
258C, CHCl3): d=7.27 (d, 3J(H,H)=7 Hz, 2H), 7.22 (d, 3J(H,H)=7 Hz,
8H), 7.22 (t, 3J(H,H)=7 Hz, 2H), 7.15 (t, 3J(H,H)=7 Hz, 1H), 7.11 (t,
3J(H,H)=7 Hz, 8H), 7.04 (t, 3J(H,H)=7 Hz, 4H), 2.84 (t, 3J(H,H)=
9 Hz, 2H), 1.41 (tt, 3J(H,H)=7 Hz, 9 Hz, 2H), 1.25 (tq, 3J(H,H)=7 Hz,
General procedures for nucleophilic substitution of the halide in penta-
organotellurium halide with organolithium reagents by triflate: THF
(25 mL) was added to a mixture of AgSO3CF3 (0.537 g, 2.09 mmol) and
pentaorganotellurium halide (1.20 mmol) at room temperature and the
reaction mixture was stirred for 10 min. After evaporation of THF in
vacuo, CH2Cl2 (25 mL) was added. Precipitated AgCl was filtered off
from the reaction mixture under an argon atmosphere, and CH2Cl2 was
evaporated from the filtrate. Et2O (50 mL) was added to the condensed
reaction mixture followed by addition of organolithium reagent
(15 mmol) at À908C. The reaction mixture was allowed to warm to room
temperature and the solvent was removed. Products were washed with
NH4Cl (aq).
(4-BrC6H4)6Te (1d): Colorless plates, m.p. >3008C; 1H NMR (CDCl3,
258C, CHCl3): d=6.85 (d, 3J(H,H)=9 Hz, 12H), 7.35 ppm (d, 3J(H,H)=
9 Hz, 12H); 13C NMR (CDCl3, 258C, CHCl3): d=123.9 (s), 131.6 (d),
134.6 (d), 147.3 ppm (s, 1J(C,Te)=37 Hz); 125Te NMR (CDCl3, 258C,
(CH3)2Te): d=476 ppm.
(4-CF3C6H4)5(4-MeOC6H4)Te (8): Colorless crystals; m.p. >2908C; 1H
NMR (CDCl3, 258C, CHCl3): d=7.52 (d, 3J(H,H)=9 Hz, 2H), 7.49 (d,
3J(H,H)=9 Hz, 8H), 7.12 (d, 3J(H,H)=9 Hz, 8H), 7.10 (d, 3J(H,H)=
9 Hz, 2H), 6.83 (d, 3J(H,H)=9 Hz, 2H), 6.77 (d, 3J(H,H)=9 Hz, 2H),
3.79 ppm (s, 3H); 19F NMR (CDCl3, 258C, CFCl3): d=À63.1 (s, 12F),
À63.3 ppm (s, 3F); 13C NMR (CDCl3, 258C, CHCl3): d=159.6 (s), 153.2
(s), 153.0 (s), 152.9 (s), 134.6 (q, 2J(C,F)=42 Hz), 134.4 (q, 2J(C,F)=
42 Hz), 134.3 (d), 133.5 (d), 133.4 (d), 125.7 (q, 1J(C,F)=289 Hz), 125.6
(q, 1J(C,F)=289 Hz), 125.6 (d), 125.5 (d), 125.4 (d), 55.3 ppm (s); 125Te
NMR (CDCl3, 258C, (CH3)2Te): d=469.9 ppm; elemental analysis calcd
(%) for C37H23F15Te + 1/2H2O: C 49.97, H 2.72; found: C 50.02, H 2.54.
3
2H), 0.78 ppm (t, J(H,H)=7 Hz, 3H); 13C NMR (CDCl3, 258C, CHCl3):
d=152.7 (s), 151.6 (s), 133.6 (d), 132.9 (d), 128.3 (d), 127.9 (d), 127.8 (d),
127.5 (d), 50.1 (s), 30.9 (s), 24.7 (s), 13.6 ppm (s); 125Te NMR (CDCl3,
258C, (CH3)2Te): d=401.9 ppm; elemental analysis calcd (%) for
C42H27F15Te + 3benzene: C 60.32, H 3.79; found: C 59.98, H 3.55.
(4-CF3C6H4)4(CH3)2Te (cis-4a): Colorless plates; m.p. 236 2378C; 1H
NMR (CDCl3, 258C, CHCl3): d=2.19 (s, 6H), 7.46 (d, 3J(H,H)=8 Hz,
4H), 7.52 (d, 3J(H,H)=8 Hz, 4H), 7.53 (d, 3J(H,H)=8 Hz, 4H),
7.56 ppm (d, 3J(H,H)=8 Hz, 4H); 19F NMR (CDCl3, 258C, CFCl3): d=
À63.0 (s, 6F), À63.1 ppm (s, 6F); 13C NMR (CDCl3, 258C, CHCl3): d=
34.5 (q, 1J(C,Te)=9 Hz), 123.8 (q, 1J(C,F)=273 Hz), 123.9 (q, 1J(C,F)=
273 Hz), 124.6 (d), 124.7 (d), 130.4 (q, 2J(C,F)=33 Hz), 130.5 (q,
2J(C,F)=33 Hz), 132.7 (d), 132.8 (d), 159.6 (s, 1J(C,Te)=87 Hz),
160.0 ppm (s, 1J(C,Te)=25 Hz); 125Te NMR (CDCl3, 258C, (CH3)2Te):
d=272 ppm; elemental analysis calcd (%) for C30H22F12Te: C 48.82, H
3.00; found: C 48.65, H 2.82.
X-ray structural analysis of 1d, cis-4a, trans-4c, trans-7a-Cl,and 9
:
CCDC-212473 (1d), CCDC-212475 (cis-4a), CCDC-212476 (trans-4c),
CCDC-212478 (trans-7a-Cl), and CCDC-212479 (and 9) contain the sup-
plementary crystallographic data for this paper. These data can be ob-
from the Cambridge Crystallographic Centre, 12 Union Road, Cambridge
CB21EZ, UK; Fax: (+44)1223-336033; or deposit@ccdc.cam.ac.uk). A
summary of the important data from the X-ray structure determinations
is given in Table 5. Data were collected at 150 K on a Mac Science
DIP2030 imaging plate equipped with graphite-monochromated MoKa ra-
diation (l=0.71073 ä). Unit cell parameters were determined by autoin-
dexing several images in each data set separately with program DENZO.
For each data set, rotation images were collected in 38 increments with a
total rotation of 1808 about f. Data were processed by using SCALE-
PACK. The structures were solved by using the teXsan system and re-
fined by full-matrix least-squares. The programs (DENZO and SCALE-
PACK) are available from Mac Science Co. Z Otwinowski, University of
Texas, Southwestern Medical Center. The program teXsan is available
from Rigaku Co.
(4-CF3C6H4)5(CH=CH2)Te (9): Colorless needles; m.p. 214 2158C; 1H
NMR (CDCl3, 258C, CHCl3): d=7.53 (d, 3J(H,H)=8 Hz, 2H), 7.51 (d,
3J(H,H)=8 Hz, 8H), 7.41 (d, 3J(H,H)=8 Hz, 2H), 7.35 (d, 3J(H,H)=
8 Hz, 8H), 6.80 (dd, 3J(H,H)=11 Hz, 18 Hz, 1H), 6.39 (d, 3J(H,H)=
11 Hz, 1H), 5.38 ppm (d, J(H,H)=18 Hz, 1H); 13C NMR (CDCl3, 258C,
3
CHCl3): d=153.9 (s, 1J(C,Te)=49 Hz), 151.6 (s, 1J(C,Te)=25 Hz), 133.6
(d), 132.9 (d), 131.5 (q, 2J(C,F)=32 Hz), 131.3 (q, 2J(C,F)=32 Hz), 129.6
(d), 125.6 (d), 125.5 (d), 125.1 (d), 123.7 (q, 1J(C,F)=271 Hz), 123.6 ppm
(q, 1J(C,F)=271 Hz); 125Te NMR (CDCl3, 258C, (CH3)2Te): d=
420.3 ppm; elemental analysis calcd (%) for C37H23F15Te + 1/2H2O: C
49.97, H 2.72; found: C 50.02, H 2.54.
Ph5(CH=CH2)Te (10): Colorless needles; m.p. 239 2408C; 1H NMR
(CDCl3, 258C, CHCl3): d=7.30 7.45 (m, 1H), 7.38 (d, 3J(H,H)=8 Hz,
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3
2H), 7.30 (t, J(H,H)=8 Hz, 8H), 7.19 (t, 3J(H,H)=8 Hz, 4H), 7.15 7.22
(m, 2H), 7.07 (d, 3J(H,H)=8 Hz, 8H), 6.85 (dd, 3J(H,H)=11 Hz, 19 Hz,
1H), 6.27 (d, 3J(H,H)=11 Hz, 1H), 5.32 ppm (d, 3J(H,H)=19 Hz, 1H).
13C NMR (CDCl3, 258C, CHCl3): d=154.2 (s, 1J(C,Te)=53 Hz), 151.6 (s,
1J(C,Te)=37 Hz), 150.1 (d), 149.8 (d), 133.6 (d), 133.2 (d), 128.3 (d),
128.1 (d), 127.5 (d), 127.3 ppm (d); 125Te NMR (CDCl3, 258C, (CH3)2Te):
d=429.5; elemental analysis calcd (%) for C32H28Te + 1/2H20: C 69.98,
H 5.32; found: C 69.88, H 5.13.
(4-CF3C6H4)5(CH2SPh)Te (11): Red solid; m.p. 152 1538C; 1H NMR
(CDCl3, 258C, CHCl3): d=7.77 (d, 3J(H,H)=7 Hz, 2H), 7.72 (d,
3J(H,H)=7 Hz, 2H), 7.6 7.7 (m, 5H), 7.68 (d, 3J(H,H)=7 Hz, 8H), 7.46
(d, 3J(H,H)=7 Hz, 8H), 3.55 ppm (s, 2H); 19F NMR (CDCl3, 258C,
CFCl3): d=À63.0 (s, 12F), À63.4 ppm (s, 3F); 13C NMR (CDCl3, 258C,
CHCl3): d=152.2 (s), 150.6 (s), 140.8 (s), 133.6 (d), 133.2 (d), 131.0 (q,
2
2J(C,F)=30 Hz), 130.4 (q, J(C,F)=30 Hz), 130.1 (d), 125.9 (d), 125.8 (d),
125.7 (d), 123.3 (q, 1J(C,F)=270 Hz), 123.0 (q, 1J(C,F)=270 Hz), 122.5
(d), 47.0 ppm (s); 125Te NMR (CDCl3, 258C, (CH3)2Te): d=420.7 ppm; el-
emental analysis calcd (%) for C42H27F15STe: C 51.6, H 2.78; found: C
49.9, H 2.67.
Ph5(CH2SPh)Te (12): Colorless crystals; m.p. 164 1658C; 1H NMR
(CDCl3, 258C, CHCl3): d=7.46 (d, 3J(H,H)=7 Hz, 2H), 7.42 (d,
3J(H,H)=7 Hz, 8H), 7.36 7.39 (m, 2H), 7.33 (t, 3J(H,H)=7 Hz, 4H),
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Chem. Eur. J. 2004, 10, 2590 2600
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