200
F.D. Rochon et al. / Inorganica Chimica Acta 346 (2003) 197Á206
/
(17), 1070w, 1055w (14), 1026m (1), 976w (5), 820w (12),
729w (13), 695w (4), 638w (6), n(SꢀO) 1120s, n(PtꢀS)
437w. 1H NMR (ppm in CD2Cl2): H2 9.441s
3J(195Ptꢀ1H)ꢁ
21 Hz, H4 8.773dd Jꢁ5.0, 2.3, H5
7.470ddd Jꢁ6.0, 4.8, 1.2 Hz, H6 8.982ddd Jꢁ5.7,
2.2.5. trans-Pt(DBzSO)(pm)I2
Yield 65%. IR (cmꢀ1): 3060w, 3032w, 2970w, 2920w,
1588s, 1503m, 1491m, 1451m, 1404s, 1375m, 1330m,
/
/
/
/
/
1170m, n(Sꢀ
(ppm in CDCl3): CH2 4.58d Jꢁ
Hz, 5.20d Jꢁ12.9 Hz, 5.48d Jꢁ
9.677s, H4 8.70m, H5 7.66m, H6 9.19m. 13C NMR
13C)ꢁ
/
O) 1129s, 872m, 695s, 479m. 1H NMR
/
/
/
12.6 Hz, 5.00d Jꢁ
/12.9
2.3, 0.9 Hz, 3J(195Ptꢀ
/
1H)ꢁ
/
30 Hz, Ha 3.860s
/
/12.3 Hz, Ph 7.45m, H2
3J(195Ptꢀ
/
1H)ꢁ
/
23 Hz. 13C NMR (ppm): C2 161.94, C4
159.17, C5 122.61 J(195Ptꢀ
3
/
13C)ꢁ
/
27 Hz, C6 160.54, Ca
(ppm): C2 163.49, C4 157.60, C5 121.80 3J(195Ptꢀ
/
/
51.83 J(195Ptꢀ
/
13C)ꢁ
/69 Hz.
30 Hz, C6 162.00, Cphenyl 128.36, 128.95, 130.11, 131.7.
2
2.2.6. trans-Pt(MeBzSO)(pm)I2
Yield 65%. IR (cmꢀ1): 3052w, 3002w, 2970w, 2922w,
1590s, 1553m, 1495w, 1465w, 1451w, 1405s, 1150m,
2.2.2. trans-Pt(TMSO)(pm)I2
Yield 61%. M. p. 121Á
209 8C dec. IR (cmꢀ1): pm:
3060w (2), 1593s, 1557m (9,10), 1468m (22), 1408s (23),
/
n(Sꢀ
/
O) 1110s, 1067w, 973m, 962m, 871w, 766m, 696s,
S) 446m. 1H NMR (ppm in CD2Cl2):
CH3 3.59s J(195Ptꢀ1H)ꢁ
23 Hz, CH2 5.07dd Jꢁ13.8,
1.2 Hz, (second peak hidden by solvent), Ph 7.49m, H2
1225w (3), 1171w (17), 1073s, 1052sh (14), 1025w (1),
636w, 478m, n(Ptꢀ
/
813w (12), 698m (4), 639m (6), n(Sꢀ
444w. 1H NMR (ppm in CD2Cl2): H2 9.468s
3J(195Ptꢀ1H)ꢁ
22 Hz, H4 8.783dd Jꢁ5.0, 2.3 Hz, H5
7.474ddd Jꢁ5.9, 4.7, 1.3 Hz, H6 9.021ddd Jꢁ6.0, 2.1,
14.1,
/
O) 1142s, n(Ptꢀ
/
S)
3
/
/
/
/
/
/
9.34s J(195Ptꢀ
/
1H)ꢁ
5.1, 2.4 Hz, H6 8.96ddd Jꢁ
1H)ꢁ34 Hz. 13C NMR (ppm): CH3 47.57
13C)ꢁ70.7 Hz, CH2 67.61 2J(195Ptꢀ13C)ꢁ
63.6 Hz, Ph 129.08, 129.18, 129.63, 131.89, C2 161.67
2J(195Ptꢀ13C)ꢁ
15 Hz, C4 158.96, C5 122.45
3J(195Ptꢀ13C)ꢁ33 Hz, C6 160.30 2J(195Ptꢀ13C)ꢁ
15
Hz.
/
22 Hz, H4 8.69dd, Jꢁ/5.1, 2.4 Hz,
3
/
/
1.1 Hz, 3J(195Ptꢀ
/
1H)ꢁ
/
30 Hz, Ha 4.067ddd Jꢁ
/
H5 7.50dd Jꢁ
/
/5.7, 2.1, 0.9
3
Hz, J(195Ptꢀ
/
/
7.1, 7.1, 3.911m, Hb 2.306m, 2.161m. 13C NMR (ppm):
2J(195Ptꢀ
/
/
/
/
C2 161.95, C4 159.14, C5 122.64 J(195Ptꢀ
/
13C)ꢁ
/
30 Hz,
3
C6 160.52, Ca 64.23 2J(195Ptꢀ
3J(195Ptꢀ13C)ꢁ
27 Hz.
/
13C)ꢁ
/
70 Hz, Cb 25.43
/
/
/
/
/
/
/
/
2.2.3. trans-Pt(DPrSO)(pm)I2
Yield 75%. M.p. 112 8C. IR (cmꢀ1): pm: 3084w (8),
3046m (2), 1593s, 1557m (9,10), 1464m (22), 1409m (23),
1223w (3), 1170w (17), 1074m, 1055w (14), 1024w (1),
2.2.7. trans-Pt(MePhSO)(pm)I2
Yield 65%. IR (cmꢀ1): 3082m, 3062m, 3020m, 3000m,
2915w, 1585s, 1548s, 1463m, 1438m, 1398s, 1302w,
814w (12), 738w (13), 699m (4), 637m (6), n(Sꢀ
n(PtꢀN) 512m, n(Ptꢀ
S) 453m. 1H NMR (ppm in
CD2Cl2): H2 9.449s J(195Ptꢀ
Jꢁ5.1, 2.1 Hz, H5 7.459ddd Jꢁ
8.990ddd Jꢁ
4.050ddd Jꢁ
5.1 Hz, Hb 2.261dddq Jꢁ
2.082dddq Jꢁ
7.4Hz. 13C NMR (ppm): C2 161.89, C4 159.04, C5
122.49 3J(195Ptꢀ13C)ꢁ
26 Hz, C6 160.53, Ca 61.71
2J(195Ptꢀ13C)ꢁ
56 Hz, Cb 17.57, Cg 12.90.
/O) 1127s,
1225w, 1170m, n(Sꢀ
/
O) 1135s, 1084m, 1062m, 1053m,
/
/
1022s, 957s, 820s, 757m, 723m, 698s, 640s, 517s, 488m,
412w, 363w. 1H NMR (ppm in CDCl3): CH3 4.11
3
/
1H)ꢁ
6.0, 4.9, 1.3 Hz, H6
1H)ꢁ
32 Hz, Ha
12.8, 11.1, 5.3 Hz, 3.592ddd Jꢁ
/
21 Hz, H4 8.764dd
3J(195Ptꢀ
3J(195Ptꢀ
7.64m, H6 9.04ddd Jꢁ
/
1H)ꢁ
/
24 Hz, Ph 7.45m, H2 9.52s
24 Hz, H4 8.78dd, Jꢁ4.9, 2.1 Hz, H5
/
/
3
1H)ꢁ
/
/
/
5.9, 2.3, 1.1 Hz J(195Ptꢀ
/
/
/
3
6.2, 2.0, 1.0 Hz, J(195Ptꢀ
/
1H)ꢁ
/
/
/12.8, 11.1,
/
33 Hz. 13C NMR (ppm): CH3 55.49, Ph 125.38, 129.31,
129.93, 133.0, C2 161.98, C4 158.78, C5 122.22, C6
160.44.
/15.1, 10.9, 7.4, 5.3 Hz,
/
15.1, 11.0, 7.4, 5.3 Hz, Hg 1.213t Jꢁ
/
/
/
/
/
3. Results and discussion
2.2.4. trans-Pt(DBuSO)(pm)I2
Yield 49%. M.p. 155Á
193 8C dec. IR (cmꢀ1): pm:
3085w (8), 3048w (2), 1594m, 1557w (9,10), 1468m (22),
/
3.1. Complexes I(R2SO)Pt(m-I)2Pt(R2SO)I
1402s (23), 1229w (3), 1169w (17), 1077sh, 1057sh (14)
The aqueous reaction of K2[PtI4] with sulfoxides does
not produce K[Pt(R2SO)I3] or Pt(R2SO)2I2 as in the
analogous chloro system. The reaction was studied with
1024sh (1), 740w (13), 699m (4), 638w (6), n(Sꢀ
n(PtꢀN) 499w, n(Ptꢀ
S) 454m. 1H NMR (ppm in
CD2Cl2): H2 9.440s J(195Ptꢀ
Jꢁ5.1, 2.1 Hz, H5 7.453ddd Jꢁ
8.983ddd Jꢁ
4.064ddd Jꢁ
5.1 Hz, Hb 2.198m, 2.000m, Hg 1.618sextuplet Jꢁ
Hz, Hd 1.027t Jꢁ
7.2 Hz. 13C NMR (ppm): C2 161.88,
C4 159.03, C5 122.48 J(195Ptꢀ
Ca 59.89
2J(195Ptꢀ13C)ꢁ
3J(195Ptꢀ13C)ꢁ
15 Hz, Cg 21.76, Cd 13.85.
/
O) 1130s,
/
/
3
/
1H)ꢁ
5.9, 5.0, 1.1 Hz, H6
5.9, 2.2, 1.0 Hz J(195Ptꢀ1H)ꢁ
30 Hz, Ha
12.7, 11.3, 5.0 Hz, 3.599ddd Jꢁ12.8, 11.1,
7.3
/
20 Hz, H4 8.753dd
R2SOꢁDMSO, tetramethylenesulfoxide (TMSO), di-n-
/
/
/
propylsulfoxide (DPrSO), di-n-butylsulfoxide (DBuSO),
dibenzylsulfoxide (DBzSO) and benzylmethylsulfoxide
(MeBzSO). A few experiments were also done on
methylphenylsulfoxide (MePhSO), although the pro-
ducts were not very stable. The reaction produces a
dark red precipitate which has been characterized by IR
and multinuclear magnetic resonance spectroscopies
and a few by elemental analysis and X-ray diffraction.
3
/
/
/
/
/
/
/
3
/
13C)ꢁ
56 Hz,
/
26 Hz, C6 160.55,
/
/
Cb 25.54
/
/