FULL PAPER
quid. Purification was done by column chromatography using silica
as stationary phase (CHCl3/MeOH, 95:5). The product HL1 was
obtained as a yellow-brown viscous oil and was finally dried under
high vacuum, yield 75% (893 mg). C15H16N2OTe (367.90): calcd.
crystals suitable for X-ray diffraction analysis were obtained by
recrystallization from CH2Cl2/MeOH (v/v 1:1) (7 and 8) or DMSO
(7).
Data for 7 (M = Pt): C15H15ClN2OPtTe (597.44): calcd. C 30.2, H
C 48.9, H 4.4, N 7.6; found C 47.6, H 4.5, N 7.0. IR: ν = 3381 (s),
˜
2.5, N 4.7; found C 30.1, H 2.5, N 4.5. IR: ν = 3049 (w), 2924 (w),
˜
3053 (m), 2930 (s), 2860 (m), 1670 (s), 1589 (m), 1524 (s), 1464 (s),
1433 (s), 1364 (w), 1288 (m), 1246 (m), 1167 (m), 1088 (w), 1063
(w), 1042 (w), 1018 (m), 997 (s), 820 (m), 733 (s), 692 (s), 621 (m),
455 (m) cm–1. 1H NMR (CDCl3): δ = 2.10 (quint, J = 7.6 Hz, 2 H,
CH2), 2.91 (t, J = 7.6 Hz, 2 H, Te-CH2), 3.52 (q, J = 6.6 Hz, 2 H,
N-CH2), 7.15–7.19 (m, 2 H), 7.23–7.27 (m, 1 H), 7.39 (ddd, J =
7.6, 4.8, 1.2 Hz, 1 H), 7.70–7.73 (m, 2 H), 7.81 (td, J = 7.7, 1.7 Hz,
1 H, Ph, py), 8.07 (br. s, 1 H, NH), 8.16 (dt, J = 7.8, 1.0 Hz, 1 H,
py), 8.50 (ddd, J = 4.8, 1.7, 0.9 Hz, 1 H, py) ppm. 13C NMR
(CDCl3): δ = 4.9 (Te-CH2), 31.7 (CH2), 40.9 (N-CH2), 111.4 (Te-
Ph), 122.1 (py), 126.1 (py), 127.6 (Ph), 129.1 (Ph), 137.3 (Ph), 138.3
(py), 147.9 (py), 149.7 (py), 164.3 (C=O) ppm. 125Te NMR
(CDCl3): δ = 483 ppm. MS (ESI+, CH2Cl2/MeOH): m/z (%) =
409.00 (13) [M + K]+, 393.02 (100) [M + Na]+, 163.09 (50) [M –
TePh]+. HRMS: m/z calcd. for [M + Na]+ 393.02175; found
393.0222.
2846 (w), 1622 (s), 1595 (s), 1476 (w), 1437 (w), 1377 (w), 1281 (w),
1250 (w), 1177 (w), 1096 (w), 1051 (w), 997 (w), 758 (w), 733 (w),
689 (w), 679 (w), 544 (w), 478 (w), 453 (w) cm–1. 1H NMR (CDCl3):
δ = 2.13–2.22 (m, 1 H, CH2), 2.48 (qd, J = 9.3, 5.4 Hz, 2 H, Te-
CH2), 2.75–2.83 (m, 1 H, CH2), 3.20 (dd, J = 14.7, 9.7 Hz, 1 H,
N-CH2), 3.78 (ddd, J = 13.0, 8.1, 5.1 Hz, 1 H, N-CH2), 7.31–7.35
(m, 2 H), 7.39–7.43 (m, 1 H), 7.56 (ddd, J = 7.3, 5.6, 1.5 Hz, 1 H),
7.86–7.88 (m, 1 H), 8.02 (dt, J = 7.7, 1.4 Hz, 1 H), 8.07 (tt, J =
5.3, 2.2 Hz, 2 H, Ph, py), 9.20–9.21 (m, 1 H, py) ppm. 13C NMR
([D6]DMSO): δ = 14.9 (Te-CH2), 32.2 (CH2), 45.5 (N-CH2), 116.7
(Te-Ph), 125.7, 128.0, 129.8, 130.2, 137.4, 141.7 (Ph, py), 144.5 (py),
152.4 (py), 172.3 (C=O) ppm. 125Te NMR ([D6]DMSO): δ = 537
(J|195Pt125Te| = 3215 Hz) ppm. 195Pt NMR ([D6]DMSO): δ =
–3450 ppm. MS (ESI+, CH2Cl2/MeOH): m/z (%) = 1815.85 (8) [3M
+ Na]+, 1218.90 (22) [2M + Na]+, 638.94 (9) [M + K]+, 620.94
(100) [M + Na]+, 598.96 (8) [M + H]+, 562.98 (9) [M – Cl]+, 484.94
(14) [M – py, – Cl]+. HRMS: m/z calcd for [M + Na]+ 620.9402;
found 620.9444.
HL2: A solution of N-[NЈ,NЈ-methyl(phenyl)aminothiocarbonyl]-
benzimidoyl chloride (1 g, 3.46 mmol) in anhydrous acetone
(10 mL) was added dropwise to a mixture of 3-(phenyltellanyl)-
propylammonium chloride (910 mg, 3.46 mmol) and NEt3 (1 mL,
7 mmol) in anhydrous acetone (5 mL). The color of the reaction
mixture changed from yellow to dark red. Stirring was continued
for 2 h at room temperature. After the suspension was cooled to
0 °C, a colorless precipitate of NEt3·HCl was filtered off and the
solvent was removed under reduced pressure. The residue was redis-
solved in CH2Cl2 (5 mL), washed with brine (3ϫ 5 mL) and the
solvent was removed again under reduced pressure. The remaining
dark-brown viscous liquid was purified by column chromatography
using silica as stationary phase (CH2Cl2). After drying under high
vacuum, the product HL2 was obtained as a dark-red viscous oil,
yield 61% (1.09 g). C24H25N3STe (515.14): calcd. C 55.9, H 4.9, N
Data for 8 (M = Pd): C15H15ClN2OPdTe (508.75): calcd. C 35.4,
H 3.0, N 5.5; found C 35.0, H 3.1, N 5.4. IR: ν = 3069 (w), 3044
˜
(w), 2994 (w), 2926 (w), 2849 (w), 1611 (s), 1585 (s), 1570 (s), 1474
(w), 1433 (w), 1373 (m), 1358 (m), 1283 (w), 1248 (w), 1171 (w),
1138 (w), 1092 (w), 1049 (w), 997 (w), 935 (w), 806 (w), 781 (w),
756 (m), 735 (m), 689 (m), 655 (w), 542 (w), 509 (w), 473 (w), 449
(w), 407 (w) cm–1. 1H NMR (CDCl3): δ = 2.06–2.16 (m, 1 H, CH2),
2.46–2.57 (m, 2 H, Te-CH2), 2.65–2.71 (m, 1 H, CH2), 3.02 (dd, J
= 14.7, 9.7 Hz, 1 H, N-CH2), 3.62 (dd, J = 14.8, 6.9 Hz, 1 H, N-
CH2), 7.33–7.37 (m, 2 H), 7.41–7.45 (m, 1 H), 7.50 (ddd, J = 7.2,
5.4, 1.6 Hz, 1 H), 7.92 (dd, J = 7.8, 1.5 Hz, 1 H), 7.98 (td, J = 7.6,
1.5 Hz, 2 H), 8.09–8.12 (m, 2 H, Ph, py), 8.93–8.95 (m, 1 H,
py) ppm. 13C NMR ([D6]DMSO): δ = 15.3 (Te-CH2), 32.2 (CH2),
45.2 (N-CH2), 118.1 (Te-Ph), 125.4, 127.6, 130.0, 130.1, 137.6,
141.6 (Ph, py), 146.1 (py), 153.8 (py), 172.2 (C=O) ppm. 125Te
NMR ([D6]DMSO): δ = 577 ppm. MS (ESI+, CH2Cl2/MeOH): m/z
(%) = 1564.66 (6) [3M + K]+, 1548.68 (31) [3M + Na]+, 1094.84
(6) [2M – H, + 2K]+, 1056.76 (21) [2M + K]+, 1040.78 (46) [2M +
Na]+, 982.83 (34) [2M – Cl]+, 586.94 (11) [M + 2K]+, 548.86 (26)
[M + K]+, 532.89 (55) [M + Na]+, 510.91 (13) [M + H]+, 474.93
(100) [M – Cl]+, 446.90 (35) [M – Cl, – (CO)]+. HRMS: m/z calcd.
for [M + Na]+ 532.8867; found 532.8875.
8.1, S 6.2; found C 52.9, H 4.7, N 7.1, S 6.3. IR: ν = 3298 (w),
˜
3061 (w), 2926 (w), 1598 (s), 1574 (s), 1533 (w), 1493 (s), 1464 (w),
1433 (s), 1362 (s), 1333 (s), 1294 (s), 1134 (w), 1099 (s), 1018 (w),
997 (w), 903 (w), 775 (w), 733 (m), 694 (s), 563 (w), 528 (w), 453
1
(w) cm–1. H NMR (CDCl3): δ = 1.83–2.01 (m, 2 H, CH2), 2.70–
2.83 (m, 2 H, Te-CH2), 3.25–3.34 (m, 2 H, N-CH2), 3.54–3.63 (m,
3 H, CH3), 7.01–7.44 (m, 13 H, Ph), 7.65 (d, J = 7.2 Hz, 2 H, Ph),
10.22 (s, 1 H, NH) ppm. 13C NMR (CDCl3): δ = 5.8 (Te-CH2),
29.8 (CH2), 43.7 (N-CH2), 53.7 (CH3), 112.4 (Te-Ph), 126.0, 126.3,
126.4, 127.0, 127.7, 127.9, 128.1, 128.5, 129.0, 129.3, 129.4, 129.5,
129.9, 130.6, 134.6, 138.5 (Ph), 145.1 (N-Ph), 155.8 (C=N), 190.1
(C=S) ppm. 125Te NMR (CDCl3): δ = 471, 475 (E/Z isomers) ppm.
MS (ESI+, CH2Cl2/MeOH): m/z (%) = 1069.12 (9) [2M + K]+,
1053.15 (55) [2M + Na]+, 556.05 (8) [M + K]+, 540.07 (47) [M +
Na]+, 516.08 (100) [M + H]+. HRMS: m/z calcd. for [M + H]+
516.0745; found 516.0765.
[PtI3(L1-κN,NЈ,Te)] (9): A solution of HL1 (37 mg, 0.1 mmol) in
CH2Cl2 (2 mL) was added dropwise to a stirred suspension of PtCl2
(27 mg, 0.1 mmol) in MeOH (2 mL). The reaction mixture was
heated to reflux until a brown precipitate of complex 7 was formed.
The suspension was treated with a solution of iodine (50 mg,
0.2 mmol) in methanol (1 mL) and stirred for a further 5 min at
room temperature. Finally, the solvent was removed and the solid
was recrystallized from CH2Cl2/CHCl3/MeOH (v/v/v 1.5:4:1.5).
Slow evaporation on air gave black blocks, yield 75% (71 mg).
C15H15I3N2OPtTe (942.70): calcd. C 19.1, H 1.6, N 3.0; found C
Synthesis of Complexes
[MCl(L1-κN,NЈ,Te)] [M = Pt (7), Pd (8)]: A suspension of HL1
(37 mg, 0.1 mmol) in CH2Cl2 (3 mL) was added dropwise to a
stirred suspension of MCl2 [27 mg (7), 18 mg (8), 0.1 mmol] in
19.1, H 1.6, N 2.9. IR: ν = 3051 (w), 2980 (w), 2924 (w), 2851 (w),
˜
MeOH (3 mL). The temperature of the reaction mixtures was kept 1670 (w), 1638 (w), 1612 (m), 1582 (s), 1568 (s), 1520 (w), 1474 (w),
at 30 °C for 1 h, whereupon clear solutions were formed. The
CH2Cl2 was evaporated and brownish-yellow solids started to pre-
1431 (m), 1406 (m), 1383 (m), 1304 (w), 1292 (w), 1277 (w), 1250
(m), 1192 (w), 1171 (w), 1144 (w), 1092 (w), 1045 (w), 1030 (m),
cipitate. The solids were filtered off, washed with a small amount of 1000 (m), 996 (w), 934 (w), 779 (w), 754 (m), 735 (s), 677 (m), 654
1
cold MeOH, and dried in high vacuum, yields of the noncrystalline
(m), 538 (w), 449 (w) cm–1. H NMR (CDCl3): δ = 2.90–3.39 (m,
products: 66% (39 mg) (7) and 77% (28 mg) (8). Orange-red single
4 H, CH2, Te-CH2), 3.63–3.84 (m, 1 H, N-CH2), 3.95–4.16 (m, 1
Eur. J. Inorg. Chem. 2015, 3748–3757
3754
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim