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R.C. Jones et al. / Polyhedron 26 (2007) 708–718
1
20.92. Found: C, 62.75; H, 7.24; N, 9.26; S, 20.68%. H
1391(w), 1373(w), 1312(w), 1279(w), 1176(w), 1154(w),
1033(m), 977(m), 897(w), 823(m), 436(w). LSIMS (m/z):
531 ([195Pt80Br2C8H11NS+Na]+ 531).
3
NMR (299.9 MHz, CDCl3, 25 ꢁC) d 8.36 (d, J = 5.1 Hz,
3
1H, H6), 7.18 (s, 1H, H3), 6.98 (d, J = 4.8 Hz, 1H, H5),
3.75 (s, 2H, CH2), 2.33 (s, 3H, C4–CH3), 2.04 (s, 3H, S–
CH3); 13C{1H} NMR (75.4 MHz, 20 ꢁC, CDCl3): d 158.5
(C2), 149.0 (C6), 148.3 (C4), 124.1 (C3), 123.2 (C5), 40.1
(CH2), 21.3 (C4–CH3), 15.4 (S–CH3). LSIMS (m/z) 152
(M ꢀ H)+ [12C8H1114N32S152].
2.3. Syntheses of complexes [PtBr2L] (L = L1 (1), L2 (2),
L3 (3), L4 (4))
2.4. Synthesis of complexes [PtBr4L] (L = L1 (5), L2 (6),
L3 (7), L4 (8))
A solution of [PtBr2(L1)] (50 mg, 0.101 mmol) in MeCN
(3 mL) was added to a concentrated solution of Br2 in CCl4
(1 mL). The red solution was allowed to stir at room tem-
perature for 25 min, Et2O was added to the red solution to
afford an orange precipitate which was then isolated and
washed with Et2O to give 5 (44 mg, 67%). Anal. Calc. for
C12H11Br4NPtS: C, 20.13; H, 1.55; N, 1.96; S, 4.48. Found:
C. 20.21; H. 1.74; N. 2.01; S. 4.37%. 1H NMR (299.9 MHz,
DMSO-d6, 25 ꢁC) d: 9.30–9.42 (m, 1H, C5H3N), 8.29–8.35
(m, 1H, C5H3N), 8.22–8.24 (m, 1H, C5H3N), 7.81–7.86 (m,
1H, C5H3N), 7.48–7.64 (m, 5H, C6H5), 5.64 (m, 2H, CH2).
IR (KBr, cmꢀ1): 3110(w), 3035(w), 1915(m), 2857(w),
1604(m), 1558(m), 1483(m), 1440(s), 1388(m), 1311(w),
1270(w), 1247(w), 1158(w), 1110(w), 1064(w), 1035(w),
896(w), 867(w), 821(w), 763(s), 750(vs), 677(m), 482(w),
419(w).
Sodium bromide (0.827 mmol) and PtCl2 (0.376 mmol)
were refluxed in MeCN (30 mL) for 24 h. The light brown
solution was filtered and the appropriate ligand
(0.381 mmol) was added. The mixture was allowed to stir
at room temperature (16 h). The MeCN volume was
reduced in a vacuum (ca. 1 mL) and Et2O added to afford
an off-white precipitate. The solid was collected and
washed with Et2O, yielding the desired compound.
[PtBr2(L1)] (1) (69%). Anal. Calc. for C12H11Br2NPtS: C,
25.91; H, 1.99; N, 2.52. Found: C, 25.50; H, 1.83; N, 2.26%.
1H NMR (299.9 MHz, DMSO-d6, 25 ꢁC) d: 9.69 (m, 1H,
C5H4N), 8.15 (m, 1H, C5H4N), 7.84 (m, 1H, C5H4N),
7.75 (m, 2H, C6H5), 7.44 (m, 3H, C6H5), 5.23, 4.84 (m,
2H, CH2). IR (KBr, cmꢀ1): 3114(w), 3085(w), 3056(w),
2968(w), 2942(s), 1892(m), 1605(m), 1476(s), 1446(s),
1394(m), 1312(w), 1268(w), 1160(w), 1111(w), 1063(w),
1021(w), 966(w), 895(w), 756(vs), 685(m), 483(m), 438(w).
LSIMS (m/z): 476 ([195Pt80BrC11H12NS]+ 476).
2.4.1. [PtBr4(L2)] (6)
The procedure used was as for [PtBr4(L1)] using L2
(70%). Anal. Calc. for C7H9Br4NPtS: C, 12.86; H, 1.39;
N, 2.14; S, 4.90. Found: C, 12.68; H, 1.40; N, 2.19; S,
1
4.20%. H NMR (299.9 MHz, DMSO-d6, 25 ꢁC) d: 9.40
(m, 1H, C5H4N), 8.23 (m, 1H, C5H4N), 7.99 (m, 1H,
C5H4N), 7.81 (m, 1H, C5H4N), 5.21, 5.02 (AB spin system,
2H, CH2), 2.69 (s, JPt–H = 18.3 Hz, 3H, CH3). IR (KBr,
[PtBr2(L2)] (2) (87%). Anal. Calc. for C7H9Br2NPtS: C,
17.02; H, 1.84; N, 2.84; S, 6.49. Found: C, 17.20; H, 2.00;
N, 2.85; S, 6.07%. 1H NMR (299.9 MHz, DMSO-d6,
25 ꢁC) d: 9.59 (m, 1H, C5H4N), 8.18 (m, 1H, C5H4N),
7.87 (m, 1H, C5H4N), 7.55 (m, 1H, C5H4N), 4.80, 4.50
(m, 2H, CH2), 2.47 (s, JPt–H = 18 Hz, 3H, CH3). IR
(KBr, cmꢀ1): 3080(w), 2992(w), 1955(s), 2898(s), 1610(s),
1474(s), 1447(m), 1423(m), 1395(m), 1318(m), 1271(m),
1166(s), 1111(w), 1062(w), 993(m), 974(m), 898(w),
862(w) 827(w), 770(vs), 709(w), 473(w), 434(w). LSIMS
(m/z): 414 ([195Pt80BrC7H9NS]+ 414).
cmꢀ1
) 3109(w), 3068(w), 3028(w), 3004(w), 2956(s),
2897(s), 1652(m), 1602(s), 1558(m), 1474(s), 1398(s),
1385(s), 1316(w), 276(m), 1243(w), 1165(w), 1110(m),
1060(w), 1033(w), 959(m), 895(w), 866(w), 825(m),
775(vs), 754(m), 692 (w), 657(w), 483(w), 436(w).
2.4.2. [PtBr4(L3)] (7)
The procedure used was as for [PtBr4(L1)] using L3
(75%). Anal. Calc. for C8H11Br4NPtS: C, 14.39; H, 1.66;
N, 2.10; S, 4.80. Found: C, 14.20; H, 1.67; N, 2.16; S,
[PtBr2(L3)] (3) (75%). Anal. Calc. for C8H11Br2NPtS: C,
18.91; H, 2.18; N, 2.76. Found: C, 18.88; H, 2.24; N, 6.03%.
1H NMR (299.9 MHz, DMSO-d6, 25 ꢁC) d: 7.62 (m, 1H,
C5H3N), 7.17 (m, 1H, C5H3N), 7.10 (m, 1H, C5H3N),
4.77 (s, br, 2H, CH2), 2.49 (s, 3H, CH3), 2.41 (s, 3H,
1
4.23%. H NMR (299.9 MHz, DMSO-d6, 25 ꢁC) d: 8.41
(m, 1H, C5H4N), 7.79 (m, 2H, C5H4N), 5.50 (s, broad,
2H, CH2), 2.70 (s, JPt–H = 18.1 Hz, 3H, CH3), 2.04 (s,
3H, CH3). IR (KBr, cmꢀ1): 2957(s), 2910(m), 1616(s),
1481(w), 1394(m), 1311(w), 1269(s), 1032(m), 980(w),
956(m), 829(m), 563(w), 443(w).
CH3). IR (KBr, cmꢀ1
) 2994(w), 2958(m), 2907(s),
1606(m), 1568(w), 1465(s), 1412(m), 1315(m), 1263(w),
1170(m), 1140(w), 1110(w), 970(m), 877(w), 796(s). LSIMS
(m/z): 531 ([195Pt80Br2C8H11NS+Na]+ 531).
2.4.3. [PtBr4(L4)] (8)
[PtBr2(L4)] (4) (81%). Anal. Calc. for C8H11Br2NPtS: C,
18.91; H, 2.18; N, 2.76. Found: C, 18.94; H, 2.32; N, 2.73%.
1H NMR (299.9 MHz, DMSO-d6, 25 ꢁC) d: 9.39 (m, 1H,
C5H3N), 7.72 (m, 1H, C5H3N), 7.38 (m, 1H, C5H3N),
4.75, 4.43 (m, 2H, CH2), 2.43 (s, JPt–H = 18.0 Hz, 3H,
CH3), 2.32 (s, 3H, CH3). IR (KBr, cmꢀ1): 2987(w),
2951(m), 2900(m), 1623(s), 1482(m), 1451(m), 1423(w),
The procedure used was as for [PtBr4(L1)] using L4
(73%). Anal. Calc. for C8H11Br4NPtS: C, 14.39; H, 1.66;
1
N 2.10. Found: C, 14.87; H, 1.84; N, 2.17%. H NMR
(299.9 MHz, DMSO-d6, 25 ꢁC) d: 9.20 (m, 1H, C5H4N),
7.84 (m, 1H, C5H4N), 7.63 (m, 1H, C5H4N), 5.12, 4.93
(AB spin system, 2H, CH2), 2.69 (s, JPt–H = 18.0 Hz, 3H,
CH3), 2.51 (s, 3H, CH3). IR (KBr, cmꢀ1): 2959(m),