Dalton Transactions
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[C6H5C(vO)CH2C(vS)C10H7], L8. Acetophenone (0.54 g, (Cb), 122.5 (Cc), 121.6 (Cf); Mass spectrum, ESI+: 285. 1 (100%,
4.50 mmol), methyl 2-thionaphthoate (0.91 g, 4.50 mmol) and [L + 2Na]+), 687.1 (5%, [BiL2]+), 949.2 (20% [BiL3 + Na]+); (LH =
NaH (0.13 g, 5.50 mmol) were reacted in THF according to GP C15H12OS).
[Bi{C6H5C(vO)CHC(vS)p-CF3–C6H4}3], B2. L2 (0.23 g,
0.75 mmol) and Bi(OtBu)3 (0.11 g, 0.25 mmol) were
reacted in THF according to GP 3 to obtain B2 as an orange
solid.
2 to obtain L8 as a red crystalline solid.
Yield: 0.75 g, 57.5%; Mp: 123 °C; FT-IR (cm−1): 1586 m,
1557 m, 1258 m, 1155 w, 901 w, 819 w, 774 m; 1H NMR
(400 MHz, CDCl3, 30 °C): δ 15.42 (s, 1H, OH), 8.33 (s, 1H, Hi),
8.05 (d, J3 7.6, 2H, Hj,q), 7.95 (m, 2H, Hl,o), 7.87 (t, J3 8.8, 2H,
Hm,n), 7.62 (s, 1H, Hf), 7.54–7.48 (m, 5H, Hb,c,d); 13C NMR
(100.1 MHz, CDCl3, 30 °C): δ 204.3 (Cg), 179.6 (Ce), 142.9 (Ch),
135.9 (Ca), 134.8 (Ck), 132.9 (Cp), 129.5 (Cj), 129.0 (Ci,q),
128.4 (Cb), 127.9 (Cl), 127.4 (Cc), 126.9 (Co), 126.8 (Cm,n),
124.5 (Cd), 110.2 (Cf); Mass spectrum, ESI+: 105.0 (100%,
[C(vO)C6H5]+), 163.1 (30% [C6H5C(vO)CH2C(vS)]+), 289.1
(20%, [LH − H]+), 291.3 (80%, [LH + H]+), 313.2 (20%, [LH +
Na]+), 335.2 (5%, [L + 2Na]+); ESI−: 289.2 (100%, [L]−). (LH =
C19H14OS).
Yield: 0.26 g, 92.0%; Mp: Dec >110 °C; FT-IR (cm−1):
1570 m, 1551 m, 1502 m, 1320 m, 1244 m, 1167 m, 1110 m,
1067 m, 1015 m, 944 m, 852 w, 824 m, 782 m, 703 m; Elemen-
tal analysis; (BiC48H30O3S3F9) Calc. (Found): C 49.28(48.66), H
3.19(2.53)%; 1H NMR (400 MHz, CDCl3, 30 °C) δ 7.93 (d, J3 8.0,
2H, Hb), 7.71 (d, J3 8.4, 2H, Hi), 7.57–7.52 (m, 3H, Hj,d), 7.41 (t,
J3 8.0, 2H, Hc), 7.37 (s, 1H, Hf); 13C NMR (100.1 MHz, CDCl3,
30 °C) δ 190.0 (Cg), 167.8 (Ce), 150.5 (Ch), 137.1 (Ca), 133.5 (Ci),
128.8 (Ck), 128.6 (Cc), 127.2 (Cd), 125.3 (Cj), 124.2 (Ci), 123.6
(Cl), 122.5 (Cb), 122.4 (Cf); Mass spectrum, ESI+: 636.9 {35%,
[CH3C(vO)CH2C(vS)C6H5], L9. Acetone (0.29 g, 5.0 mmol), [(L)2 + Na]+}, 823.0 (95%, [BiL2]+), 1153.2 (15%, [BiL3 + Na]+);
ethyl thiobenzoate (0.83 g, 5.0 mmol) and NaH (0.13 g, ESI−; 306.9 (100%, [L]−), 1165.1 (15%, [BiL3 + Cl]−), 1437.3
5.50 mmol) were reacted in THF according to GP 2 to obtain (20%, [BiL4]−); (LH = C16H11OSF3).
[Bi{p-MeOC6H4C(vO)CHC(vS)C6H5}3], B3. L3 (0.41 g,
1.50 mmol) and Bi(OtBu)3 (0.22 g, 0.50 mmol) were reacted in
THF according to GP 3 to obtain B3 as a yellow solid.
L9 as a dark purple semi liquid.
Yield: 0.46 g, 51.7%; FT-IR (cm−1): 1670 m, 1604 m,
1308 m, 1208 m, 1149 w, 1073 w, 1021 w, 767 w; 1H NMR
(400 MHz, CDCl3, 30 °C): δ 14.35 (s, 1H, OH), 8.12 (d, J3 8.8,
2H, Hf), 7.62 (t, J3 8.8, 2H, Hg), 7.50 (t, 1H, Hh), 7.07 (s, 1H,
Hc), 2.29 (s, 3H, Ha); 13C NMR (100.1 MHz, CDCl3, 30 °C): δ
204.5 (Cd), 184.8 (Cb), 133.2 (Ce), 130.9 (Cf), 129.2 (Cg), 128.4
(Ch), 110.3 (Cc), 68.8 (Ca); Mass spectrum, ESI+: 177.1 (100%,
[LH − H]+), 265.2 (65%, [LH + EtOH + H2O + Na]+), 377.2 {5%,
[(L)2 + Na]+}. (LH = C10H10OS).
Yield: 0.44 g, 86.0%; Mp: Dec >120 °C; FT-IR (cm−1):
1584 m, 1550 m, 1306 w, 1240 m, 1166 m, 1116 m, 1024 m,
940 m, 821 m, 766 m, 696 m; Elemental analysis;
(BiC48H39O6S3) Calc. (Found): C 56.52(56.51), H 4.15(4.05)%;
1H NMR (400 MHz, CDCl3, 30 °C): δ 7.93 (d, J3 8.8, 2H, Hb),
7.66 (d, J3 5.6, 2H, Hi), 7.36–7.28 (m, 3H, Hj,k), 7.26 (s, 1H, Hf),
6.84 (d, J3 8.8, 2H, Hc), 3.85 (s, 3H, Hl); 13C NMR (100.1 MHz,
CDCl3, 30 °C) δ 188.3 (Cg), 168.6 (Ce), 163.3 (Cd), 147.6 (Ch),
130.9 (Ca), 130.7 (Ci), 129.3 (Cj), 129.1 (Ck), 128.2 (Cb), 121.5
(Cc), 113.8 (Cf), 55.6 (Cl); Mass spectrum, ESI+: 746.9 (100%,
[BiL2]+), 792.4 (15%, [BiL2 + EtOH]+), 1199.3 (10%, [BiL3 + H +
Synthesis of bismuth(III) thioxoketones
GP 3: reactions with Bi(OtBu)3. All the manipulations were
carried out under standard Schlenk conditions. Bi(OtBu)3 (one
equivalent) dissolved in THF was added to a THF solution of
thioxoketone (three equivalent) which was already cooled to
−80 °C. This was stirred over night by the time the reaction
D1-DMSO]+); ESI−: 269.1 (100%, [L]−), 1051.3 (5%, [BiL3
+
Cl]−); (LH = C16H14O2S).
[Bi{p-MeOC6H4C(vO)CHC(vS)p-CF3–C6H4}3], B4. L4 (0.25 g,
temperature reached to room temperature. In the situations 0.75 mmol) and Bi(OtBu)3 (0.11 g, 0.25 mmol) were reacted in
where the product precipitates, this was filtered and washed THF according to GP 3 to obtain B4 as a yellow solid.
with diethyl ether and ethanol to remove any unreacted
Yield: 0.23 g, 74%; Mp: Dec >105 °C; FT-IR (cm−1): 1582 m,
Bi(OtBu)3 and acid. In the circumstances where the product is 1560 m, 1319 m, 1243 m, 1168 m, 1120 w, 1062 m, 1014 m,
soluble in THF, this was isolated by removing the solvent 941 m, 818 m, 760 m, 699 m; Elemental analysis;
under vacuum and washing with ether and ethanol.
[Bi{C6H5C(vO)CHC(vS)C6H5}3], B1. L1 (0.36 g, 1.50 mmol)
and Bi(OtBu)3 (0.22 g, 0.50 mmol) were reacted in
THF according to GP 3 to obtain B1 as an orange crystalline
solid.
(BiC51H36O6S3F9) Calc. (Found): C 48.61(48.20), H 3.44(2.77)%;
1H NMR (400 MHz, CDCl3, 30 °C): δ 7.95 (d, J3 9.2, 2H, Hb),
7.69 (d, J3 8.4, 2H, Hj), 7.54 (d, J3 8.4, 2H, Hi), 7.34 (s, J3 1H,
Hf), 6.88 (d, J3 9.2, 2H, Hc), 3.87 (s, 3H, Hl); 13C NMR
(100.1 MHz, CDCl3, 30 °C): δ 188.5 (Cg), 166.0 (Ce), 163.8 (Cd),
150.7 (Ch), 131.1 (Ca), 128.8 (Ci), 125.3 (Cb,j), 125.2 (Ck), 122.8
(Cm), 122.7 (Cc), 114.0 (Cf), 55.6 (Cl); Mass spectrum, ESI+:
696.9 {12%, [(L)2 + Na]+}, 882.9 (100%, [BiL2]+), 1243.1 (5%,
[BiL3 + Na]+); (LH = C17H13O2SF3).
Yield: 0.33 g, 71.0%; Mp: Dec >120 °C; FT-IR (cm−1): 1566 s,
1499 s, 1299 m, 1249 s, 1177 m, 1055 m, 1024 m, 999 m,
942 m, 808 m, 784 s, 757 m, 693 s, 668 s; Elemental analysis;
(BiC45H33O3S3·2H2O) Calc. (Found): C 55.95(55.21), H 4.17
1
(3.50)%; H NMR (400 MHz, CDCl3, 30 °C): δ 7.92 (d, J3 10.0,
[Bi{C5H4NC(vO)CHC(vS)C6H5}3], B5. L5 (0.36 g, 1.5 mmol)
2H, Hb), 7.71 (d, J3 8.8, 2H, Hi), 7.57 (t, J3 9.2, 1H, Hd), and Bi(OtBu)3 (0.22 g, 0.5 mmol) were reacted in THF accord-
7.40–7.31 (m, 5H, Hc,j,k), 7.36 (s, 1H, Hf); 13C NMR ing to GP 3 to obtain B5 as a yellow brown solid.
(100.1 MHz, CDCl3, 30 °C): δ 189.7 (Cg), 170.3 (Ce), 147.3 (Ca),
Yield: 0.32 g, 68.1%; Mp: Dec >160 °C; FT-IR (cm−1):
138.9 (Ch), 132.6 (Ck), 128.8 (Cd), 128.6 (Ci), 128.5 (Cj), 128.3 1579 m, 1563 m, 1557 s, 1305 w, 1233 m, 1279, 1078 m,
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Dalton Trans.