U. Hernández-Balderas et al. / Polyhedron 90 (2015) 165–174
167
3
3
H5-H4 = 7.31 Hz). 1H NMR (DMSO-d
(
dd, 1H, H5,
J
H5-H6 = 7.55,
J
6
)
(dec.). Yellow single crystals of 2 were obtained from a saturated
OPtÁ1.3CH
acetone solution. Anal. Calc. for C12 CN: C,
33.81; H, 3.10. Found: C, 33.71; H, 3.34%. ESI-HRMS: calcd. for C12-
3
4
d = 7.08 (dd, 1H, H6,
J
H6-H5 = 7.72,
H4-H3 = 7.99 Hz); 6.72 (dd, 1H, H3,
H3-H5 = 1.20 Hz); 6.50 (ddd, 1H, H5,
J
H6-H4 = 1.32 Hz); 7.01 (dd,
H12Cl
2
N
2
3
3
3
1
H, H4,
J
H4-H5 = 7.44,
J
3
4
3
+
J
J
H3-H4 = 7.99,
H5-H4 = 7.44,
J
J
H5-H6 = 7.72,
2 2
H12Cl N NaOPt [M+Na] 487.9867; found 488.9865; error 3.1 ppm.
3
4
). 13C NMR
À1
J
H5-H3 = 1.20 Hz); 5.30 (s, 2H, NH
) d = 149.0 (C2); 133.8 (C6); 129.5 (C4); 117.8
C5); 116.8 (C1); 115.6 (C3).
2
IR (KBr cm
)
m
)
= 1592, 1490 (C@C); 1209 (C–O–C). Raman
= 3,085 (C–H); 1603 (C@C); 1227 (C–O–C);
) d = 7.83 (d, 1H, H3,
),
H5-H4 = 7.25 Hz). C{ H} NMR
) d = 150.1 (C2); 136.5 (C1); 126.8 (C4); 126.6
C5); 123.7 (C3); 123.6 (C6).
À1
1
(
(
DMF-acetone-d
6
(420 mW, cm
m
324 (Pt–Cl). H NMR (DMF-acetone-d
6
3
J
H3-H4 = 8.06 Hz); 7.25 (m, 2H, H4, H6); 7.60 (s, br., 2H, NH
2
.12 (dd, 1H, H5,
DMF-acetone-d
2
2
.3. Synthesis of the palladium(II) complexes
.3.1. General procedure
3
3
13
1
7
(
(
JH5-H6 = 8.00,
J
6
2 2
To a solution of [Pd(MeCN) Cl ] in acetonitrile at 0 °C the corre-
1
2
sponding L or L ligand was added; the reaction mixture was stir-
red for 24 h. Then, the solution was warmed to room temperature
and the solid obtained was filtered by suction.
2
.4.3. Synthesis of [Pt{
Pt(CH CN) Cl ] [0.10 g (0.29 mmol)], acetonitrile (20 mL), 2
0.062 g (0.29 mmol)]. Yield: 92% (0.13 g, 0.26 mmol). M. p.:
2 6 4 2 2
jN,jS-(NH -C H ) S}Cl ] (5)
[
3
2
2
[
2
5
4
3
44 °C (dec.). Green crystals from a saturated acetone solution of
2
2
.3.2. Synthesis of [Pd{
j
N-(NH
2
-C
6
H
4
)
2
O}Cl
2
] (1)
+
were obtained. ESI-HRMS: calcd. for C12
H
12ClN
2
PtS [MÀCl+1]
[
Pd(MeCN) Cl
2
2
] [0.065 g (0.25 mmol)], cold acetonitrile (10 mL),
À1
46.00521, found 516.9418, error 2.5 ppm. IR (KBr cm
) m = 3440,
and 1 [0.05 (0.25 mmol)]. The yellow solid was washed with ace-
tonitrile (2 Â 3 mL). Yield: 95% (0.089 g, 0.236 mmol). Orangish-
yellow single crystals of 1 were obtained from a saturated DMSO
solution. M. p.: 254 °C (dec.). Anal. Calc. for C10
C, 36.90; H, 3.98; N 6.15. Found: C, 36.88; H, 3.93; N, 5.78%. IR
1
146 (N–H); 1618, 1480 (C@C).
H
NMR (DMF-acetone-d
6
)
d = 8.66 (s, br., 2H, NH
2
), 8.24 (s, br., 2H, NH
2
), 7.65 (d, 1H, H3,
3
3
4
J
H3-H4 = 7.80 Hz); 7.61 (dd, 1H, H12,
J
H12-H11 = 7.94,
H12-H10
J =
H12Cl
2
N
2
OPdÁC
2 6
H OS:
3
4
1
.27 Hz); 7.52 (dd, 1H, H6,
J
H6-H5 = 7.88,
JH6-H4 = 1.00 Hz);
3
3
4
7.43 (ddd, 1H, H4, JH4-H5 = 7.57, JH4-H3 = 7.80, JH4-H6 = 1.12 Hz); 7.33
À1
(
(
(
KBr cm
420 mW, cm
)
m
= 1620, 1490 (C@C); 1189 (C–O–C). Raman
3
3
4
(
ddd, 1H, H5,
J
H5-H4 = 7.57,
J
H5-H6 = 7.88,
J
H5-H3 = 1.00 Hz); 7.19
À1
)
m
= 3070 (N–H); 1601 (C@C); 440 (Pd–N); 319
d = 7.83 (dd, 1H, H3,
H3-H5 = 1.20 Hz); 7.25 (m, 2H, H4, H6); 7.11 (ddd,
3
3
4
(
ddd, 1H, H10,
J
H10-H11 = 7.65,
J
H10-H9 = 8.13,
J
H10-H12 = 1.30 Hz);
1
Pd–Cl).
H
6
NMR (DMF-acetone-d )
3
4
6
.86 (dd, 1H, H9, JH9-H10 = 8.13, JH9-H11 = 1.00 Hz); 6.62 (ddd. 1H,
3
4
J
H3-H4 = 8.20,
J
3
3
4
13
1
H11,
JH11-H10 = 7.65,
J
H11-H12 = 7.94,
J
H10-H12 = 1.00 Hz). C{ H}
) d = 149.3 (C8); 146.6 (C2); 135.5 (C12);
34.6 (C1); 133.3 (C10); 131.9 (C4); 131.3 (C6); 130.0 (C5); 127.2
C3); 117.6 (C11); 117.5 (C9); 112.8 (C7).
3
3
4
13
1
1
H, H5,
J
H5-H6 = 7.80,
JH5-H4 = 7.60,
J
H5-H3 = 1.20 Hz).
) d = 149.8 (C2); 136.0 (C1); 126.9 (C4);
26.7 (C5); 123.9 (C3); 123.6 (C6).
C{ H}
NMR (DMF-acetone-d
1
(
6
NMR (DMF-acetone-d
1
6
2
2
.3.3. Synthesis of [Pd{
j
2 6 4 2 2
N-(NH -C H ) S}Cl ] (3) and [Pd{jN,jS-
2
2
.5. Synthesis of the platinum(IV) complexes
(
NH
2 6
-C H
4 2
) S}Cl
2
] (4)
[
Pd(MeCN)
2
Cl
2
] [0.12 g (0.46 mmol)], cold acetonitrile (10 mL),
[0.10 g (0.46 mmol)]. Yellow solid, Yield: 94% (0.17 g,
.44 mmol). NMR spectra of the yellow solid displayed the forma-
23
tion of 3 and 4 as a mixture in a 70:30 ratio. Anal. Calc. for C24H -
2
.5.1. Synthesis of [Pt{
A mixture of K
0.050 g, 0.230 mmol) in 10 mL of methanol was refluxed for
0 min, then 4 mL of water were added. The solution was refluxed
j
N,j
2 6 4 6 4 3
S-(NH -C H )S(NH-C H )}Cl ] (6)
2
0
2
[PtCl
6
]Á6H O (0.112 g, 0.230 mmol) and 2
2
(
3
Cl
cm
cm
4
N
4
Pd
) m
)
2
S
2
: C, 36.62; H, 3.07. Found: C, 36.05; H, 3.06%. IR (KBr
: 3455, 3338 (N–H); 1611, 1472 (C@C). Raman (420 mW,
m = 3343 (NH); 1585 (C@C). From a saturated acetonitrile
À1
À1
for 30 min and then cooled to room temperature; the suspension
was filtered by suction and the brown solid obtained was washed
with acetone (3 Â 5 mL). On the other hand, the filtered MeOH/wa-
solution of the yellow solid were obtained red crystals for 3, m.
p.: 239–241 °C (dec.), and orange crystals for 4, which do not melt
below 250 °C.
Complex 3 was observed as the minor product. H NMR (DMF-
) d = 7.98 (d, 1H, H3,
H4-H3 = JH4-H5 = 7.82 Hz), 7.25 (m, 1H, H5), 7.04 (d, 1H, H6,
C{ H} NMR (DMF-d
37.5(C6), 131.5 (C4), 126.5 (C3), 123.8 (C5), 122.0 (C1). 4 (main
2 4
ter solution was dried with Na SO and evaporated to dryness,
yielding a brown solid. Overall, the yield of the brown solid was
35% (0.042 g, 0.081 mmol). M. p.: 134–136 °C (dec.). From a
saturated acetone solution were obtained brown crystals of 6. Anal.
Calc. for C12H11Cl N SPtÁC H O: C, 31.34; H, 2.98. Found: C, 31.38;
1
3
d
7
JH3-H4 = 7.82 Hz), 7.37 (dd, 1H, H4,
3
3
J
3
2
À1
3
6
1
3
13
1
H, 2.98%. IR (KBr cm
) m: 2921 (C–H); 1537, 1479 (C@C). H NMR
J
H6-H5 = 8.31 Hz).
7
)
d = 145.5 (C2),
3
(
acetone-d ) d = 8.08 (d, 1H, H3, JH3-H4 = 8.07 Hz); 7.47 (d, br., 1H,
6
1
3
3
3
1
H6, JH6-H5 = 7.45 Hz); 7.32 (dd, 1H, H5, JH5-H6 = 7.45, JH5-H4 =
7.68 Hz); 7.15 (t, vbr., 1H, H4).
d = 133.3 (C5); 131.5 (C3); 126.3 (vbr., C6); not observed (C1, C2,
and C4).
7
compound). H NMR (DMF-d ) d = 7.60 (m, 4H, H3, H4, H6, H12),
1
3
1
3
3
C{ H} NMR (acetone-d6)
7
6
7
1
.48 (dd, 1H, H5,
J
H5-H6 = JH5-H4 = 7.34 Hz), 7.25 (m, 2H, H10),
JH9-H10 = 7.82 Hz), 6.65 (dd, 1H, H11, J =
H11-H12
JH11-H10 = 7.34 Hz). C{ H} NMR (DMF-d ) d = 149.5 (C8),
7
45.6 (C2), 135.4 (C12), 132.8 (C10), 132.5 (C1), 131.7 (C4), 131.6
3
3
.94 (d, 1H, H9,
3
13
1
.82,
2
2.5.2. Synthesis of [Pt{
j
N,j
2 6
S-(NH -C H
4 2
) S}Cl
3
]Cl (7)
(
C6), 129.5 (C5), 131.5 (C3), 118.0 (C9), 117.3 (C11), 113.8 (C7).
2
2 6
(0.063 g, 0.290 mmol) was added to a solution of H [PtCl ]-
2
2
.4. Synthesis of the platinum(II) complexes
.4.1. General procedure
Á6H O (0.150 g, 0.290 mmol) in 10 mL of methanol at room tem-
2
perature. The mixture was stirred for 24 h; then, the suspension
was filtered and the yellow solid obtained was washed with ace-
tone (2 Â 5 mL). Yield 79% (0.127 g, 0.230 mmol). M. p.: 149 °C
(dec.). From a saturated acetone solution of 7 were obtained yellow
2 2
To a solution of [Pt(MeCN) Cl ] in hot acetonitrile (80 °C) the
corresponding L or L2 ligand was added; the reaction mixture
was stirred for 72 h in the case of 2, and 24 h for 5. Then, the solu-
tion was cooled to room temperature and the solid obtained was
filtered by suction.
1
+
crystals. ESI-HRMS: calcd. for C12H12Cl N PtS [M] 515.9429, found
3
À1
2
2
) m ); 1,547,
: 2, 750 (N–H+
516.9418, error 2.5 ppm. IR (KBr cm
1
1,478 (C@C). H NMR (DMF-acetone-d ) d = 8.51 (d, 1H, H3,
6
3
3
J
H3-H4 = 7.67 Hz); 7.73 (d, 1H, H6, JH6-H5 = 7.64 Hz); 7.59 (dd, 1H,
2
3
3
2
.4.2. Synthesis of [Pt{
Pt(MeCN) Cl
0.06 g (0.30 mmol)]. Yield: 74% (0.08 g, 0.22 mmol). M. p.: 176 °C
j
N-(NH -C
2 6
4 2
H ) O}Cl
2
] (2)
H5,
J
H5-H6 = 7.64,
J
H5-H4 = 7.20 Hz); 7.52 (t, vbr., 1H, H4), 3.70
1
[
2
2
] [0.08 g (0.30 mmol)], hot acetonitrile (10 mL), 1
(s, br., 2H, NH
H3,
2
). H NMR (DMF-acetone-d , 40 °C) d = 8.52 (d, 1H,
6
3
3
[
J
H3-H4 = 8.00 Hz); 7.76 (d, 1H, H6,
JH6-H5 = 8.00 Hz); 7.60