J. Rodríguez et al. / Journal of Organometallic Chemistry 694 (2009) 2467–2475
2473
(C@O) = 1735, d(C@N) = 1607. MS-MALDI TOF (+) m/z:
[M+H]+ = 590.0, [MꢁMe]+ = 574.0, [MꢁMe-SMe2]+ = 512.0. Anal.
Calc. for C20H24ClNO2PtS: C, 40.78; H, 4.11; N, 2.38; S, 5.44%.
Found: C, 40.9; H, 4.3; N, 2.4; S, 5.7%.
[PtMe{j
2-(C,N)-4-ClC6H3CH=NCH(iPr)CO2Me}(PPh3)] (3c). Com-
pound 3c was obtained using the same procedure than that de-
scribed above from 79 mg (0.150 mmol) of 2c. Yield: 78 mg
(72%). 1H NMR (400 MHz), d: 8.99 (s, 1H, 3J(Pt–H) = 55.9, H4),
7.77 (dd, 1H, 3J(Pt–H) = 53.6, 4J(P–H) = 5.8, J(H–H) = 2.0, H1),
7.65–7.75 (m, 6H, PPh3 ortho), 7.35–7.5 (m, 10H, H3, PPh3 meta
and para), 7.10 (dd, 1H, 3J(H–H) = 8.0, 4J(H–H) = 2.0, H2), 3.70 (d,
1H, 3J(Pt–H) = 11.6, 3J(H–H) = 9.6, H5), 3.41 (s, 3H, CO2Me), 1.92
(m, 1H, H6), 0.76 (d, 3H, 2J(Pt–H) = 82.3, J(P–H) = 7.4, Me), 0.47 (d,
3H, 3J(H–H) = 6.7, H7), 0.44 (d, 3H, 3J(H–H) = 6.6, H7´ ). 31P{1H}
NMR (121.4 MHz) d: 30.74 (s, 1J(Pt–P) = 2258.3). 195Pt NMR
[PtMe{
Compound 2e was obtained using an analogous procedure than
that described above using 203 mg (0.35 mmol) of [PtMe2(
j
2-(C,N)-4-ClC6H3CH@NCH(C6H5)CO2Me}(SMe2)]
(2e).
l
-
SMe2)]2 and 200 mg (0.70 mmol) of imine 1e and anhydrous
diethyl ether as solvent. The mixture was stirred at room temper-
ature for 16 h and after filtration, the solvent was removed on a
rotatory evaporator to yield an orange solid. Yield: 322 mg
(89%). 1H NMR (400 MHz), d: 8.54 (s, 1H, 3J(Pt–H) = 53.3, H4),
7.76 (d, 1H, 4J(H–H) = 2, J(Pt–H) = 66.3, H1), 7.34–7.43 (m, 5H,
H6, H7 and H8), 7.28 (d, 1H, 3J(H–H7) = 8, H3), 7.03 (dd, 1H,
4J(H–H) = 2, 3J(H–H) = 8, H2), 6.08 (s, 1H, H5), 3.80 (s, 3H, CO2Me),
2.24 (s, 6H, 3J(Pt–H) = 27.6, SMe2), 1.04 (s, 3H, 2J(Pt–H) = 82.6,
Me). 195Pt NMR (53.8 MHz) d: ꢁ4017.3 (s). ESI-MS {H2O:CH3CN
(1:1)}, m/z (%): [MꢁCl]+ = 522.06. Anal. Calc. for C19H22ClNO2PtS:
C, 40.82; H, 3.97; N, 2.51; S, 5.74%. Found: C, 40.8; H, 4.0; N,
2.5; S, 5.3%.
(53.8 MHz) d: ꢁ4254.3 (d, 1J(Pt–P) = 2258.8). IR (KBr),
m
(cmꢁ1):
t
(C@O) = 1742, t(C@N) = 1619, PPh3 (q-X sensitive) = 1095. MS-
MALDI TOF (+) m/z: [M+H]+ = 723.9, [MꢁMe]+ = 708.9. Anal. Calc.
for C32H33ClNO2PPt: C, 53.00; H, 4.59; N, 1.93. Found: C, 52.4; H,
4.2; N, 1.9%.
[PtMe{j
2-(C,N)-4-ClC6H3CH@NCH(CH2C6H4-(4’-OH))CO2Me}(PPh3)]
(3d). Compound 3d was obtained using the same procedure than
that described above from 88 mg (0.150 mmol) of 2d. Yield:
77 mg (65%). 1H NMR (400 MHz), d: 8.50 (s, 1H, 3J(Pt–H) = 53.8,
H4), 7.79 (dd, 1H, 3J(Pt–H) = 52.3, 4J(P–H) = 5.7, 4J(H–H) = 1.9, H1),
7.68–7.76 (m, 6H, PPh3 ortho), 7.35–7.5 (m, 10H, H3, PPh3 meta
and para), 7.01 (dd, 1H, 3J(H–H) = 8.0, 4J(H–H) = 2.0, H2), 6.53 (d,
2H, 3J(H–H) = 8.5, H7), 6.37 (d, 2H, 3J(H–H) = 8.5, H8), 4.81 (br s,
1H, OH), 4.31 (dd, 1H, 3J(H–H) = 8.3, 4J(H–H) = 4.4, H5), 3.29 (s,
3H, CO2Me), 2.72 (dd, 1H, 2J(H–H) = 13.7, 3J(H–H) = 4.4, H6), 2.44
(dd, 1H, 2J(H–H) = 13.7, 3J(H–H) = 8.4, H6´ ), 1.08 (d, 3H, 2J(Pt–
H) = 82.8, J(P–H) = 7.6, Me). 31P{1H} NMR (121.4 MHz) d: 30.85 (s,
[PtMe{
Compound 2f was obtained using the same procedure than that de-
scribed for 2e using 202 mg (0.35 mmol) of [PtMe2( -SMe2)]2 and
j
2-(C,N)-4-ClC6H3CH@NCH(CH2C6H5)CO2Me}(SMe2)] (2f).
l
212 mg (0.71 mmol) of imine 1f. Yield: 377 mg (94%). 1H NMR
(300 MHz) d: 8.35 (s, 1H, 3J(Pt–H) = 53.2, H4), 7.60 (d, 1H, J(Pt–
H) = 67.6, H1), 7.16–7.21 (m, 6H, H3, H7, H8 and H9), 6.95 (dd, 1H,
4J(H–H) = 1.7, 3J(H–H) = 7.9, H2), 4.92 (t, 1H, 3J(H–H) = 7.0, H5),
3.63 (s, 6H, CO2Me), 3.34 (dd, 1H, 2J(H–H) = 15,3; 3J(H–H) = 6.7,
H6), 3.19 (dd, 1H, 2J(H–H) = 13.6; 3J(H–H) = 7.2, H6’), 2.35 (s, 3H,
3J(Pt–H) = 27.7, SMe2), 1.01 (s, 3H, 2J(Pt–H) = 81.5, Me). 195Pt NMR
(53.8 MHz) d: ꢁ4025.3 (s). ESI-MS {H2O:CH3CN (1:1)}, m/z (%):
[MꢁCH3]+ = 557.07. Anal. Calc. for C19H22ClNO2PtS: C, 41.92; H,
4.22; N, 2.44; S, 5.60. Found: C, 42.0; H, 4.3; N, 2.5; S, 5.4%.
1J(Pt–P) = 2276.9).
IR
(KBr),
m
(cmꢁ1):
t
(C@O) = 1734,
t
(C@N) = 1612, PPh3 (q-X sensitive) = 1096. MS-MALDI TOF (+)
m/z:
[M+H]+ = 788.2,
[MꢁMe]+ = 774.2.
Anal.
Calc.
for
C36H33ClNO3PPt: C, 54.79%; H, 4.21%, N, 1.77%. Found: C, 55.0; H,
4.5; N, 1.8%.
[PtMe{
j
2-(C,N)-4-ClC6H3CH@NCH2CO2Me}(PPh3)] (3a). A mixture
[PtMe{
j
2-(C,N)-4-ClC6H3CH@NCH(C6H5)CO2Me}(PPh3)]
(3e).
of 2a (0.150 mmol, 72 mg) and PPh3 (0.150 mmol, 39 mg) in 20 mL
of acetone was stirred at room temperature for 2 h. The resulting
suspension was filtered through celite and the filtrate was concen-
trated to dryness on a rotatory evaporator to give an orange solid,
after addition of diethyl ether. The solid was washed with diethyl
ether and dried to obtain 3a. Yield: 46 mg (45%). 1H NMR
(400 MHz), d: 8.56 (s, 1H, 3J(Pt–H) = 50.8, H4), 7.80 (dd, 1H, 3J(Pt–
H) = 54.0, 4J(P–H) = 5.8, 4J(H–H) = 1.9, H1), 7.6–7.75 (m, 6H, PPh3
ortho), 7.35–7.50 (m, 10H, H3, PPh3 meta, para), 7.11 (dd, 1H,
3J(H–H) = 8.0, 4J(H–H) = 2.0, H2), 3.93 (s, 2H, 3J(Pt–H) = 11.6, H5),
3.36 (s, 3H, CO2Me), 0.77 (d, 3H, 2J(Pt–H) = 83.0, 3J(P–H) = 7.5,
Me). 31P{1H} NMR (121.4 MHz) d: 29.68 (s, 1J(Pt–P) = 2288.7).
195Pt NMR (53.8 MHz) d: ꢁ4288.8 (d, 1J(Pt–P) = 2276.5). IR (KBr),
Compound 3e was obtained using the same procedure than that
described above from 273 mg (0.52 mmol) of 2e. Yield: 376 mg
(95%). 1H NMR (300 MHz), d: 8.65 (s, 1H, J(Pt–H) = 52.9, H4),
7.69–7.80 (m, 6H, PPh3 ortho), 7.41–7.04 (m, 16H, Harom), 6.62 (d,
1H, 3J(H–H) = 7, H3), 5.31 (s, 1H, H5); 3.39 (s, 3H, CO2Me), 0.81 (d,
3H, J(Pt–H) = 83.1, 3J(Me–P) = 7.6, Me). 31P{1H} NMR (121.4 MHz,
CHCl3) d: 31.92 (s, J(Pt–P) = 2262.1). 195Pt NMR (53.8 MHz), d:
ꢁ4266.5 (d, 1J(Pt–P) = 2264.3). ESI-MS {H2O:CH3CN (1:1)}, m/z
(%): [M+H]+=759.16; [2 M+Na]+ = 1539.30. Anal. Calc. for
C35H31ClNO2PPt: C, 55.38; H, 4.12; N, 1.85. Found: C, 56.0; H, 4.1;
N, 1.9%.
[PtMe{j
2-(C,N)-4-ClC6H3CH@NCH(CH2C6H5)CO2Me}(PPh3)] (3f).
Compound 3f was obtained using the same procedure than that
described above from 286 mg (0.50 mmol) of 2f. Yield: 376 mg
(98%). 1H NMR (300 MHz), d: 8.53 (s, 1H, 4J(Pt–H) = 53.8, H4),
7.69–7.85 (m, 6H, PPh3 ortho), 7.45–7.05 (m, 16H, Harom), 6.50
(dd, 1H, 3J(H–H) = 7.9, 4J(H–H) = 1.3, H2), 4.36 (dd, 1H, 3J(H–
H) = 8.7, 3J(H–H) = 4.4, H5), 3.27 (s, 3H, CO2Me), 2.80 (dd, 1H,
2J(H–H) = 13.7; 3J(H–H) = 4.4, H6), 2.53 (dd, 1H, 2J(H–H) = 13.5;
3J(H–H) = 8.7, H6’), 0,79 (d, 3H, J(Pt–H) = 82.6, 3J(P–H) = 7.6, Me).
31P{1H} NMR (121.4 MHz) d: 32.86 (s, 1J(Pt–P) = 2269.1). 195Pt
NMR (86.1 MHz), d: ꢁ4241.6 (d, 1J(Pt–P) = 2270.4). ESI-MS
{H2O:CH3CN (1:1)}, m/z (%): [M+H]+ = 774.17. Anal. Calc. for
C36H33ClNO2PPt: C, 55.92; H, 4.30; N, 1.81. Found: C, 56.3; H, 4.4;
N, 1.9%.
m
(cmꢁ1):
tive) = 1096.
t
(C@O) = 1748, t(C@N) = 1623, PPh3 (q-X sensi-
MS-MALDI
TOF
(+)
m/z:
[M+H]+ = 681.0,
[MꢁMe]+ = 668.0. Anal. Calc. for C29H27ClNO2PPt: C, 50.59; H,
3.98; N, 2.02. Found: C, 50.7; H, 4.2; N, 2.1%.
[PtMe{j
2-(C,N)-4-ClC6H3CH@NCH(Me)CO2Me}(PPh3)] (3b). Com-
pound 3b was obtained using the same procedure than that de-
scribed above from 75 mg (0.150 mmol) of 2b. Yield: 37 mg
(35%). 1H NMR (400 MHz), d: 8.78 (s, 1H, 3J(Pt–H) = 53.2, H4),
7.66 (dd, 1H, 3J(Pt–H) = 53.8, J(P–H) = 5.8, 4J(H–H) = 2.0, H1),
7.65–7.75 (m, 6H, PPh3 ortho), 7.35–7.50 (m, 10H, H3, PPh3 meta
and para), 7.11 (dd, 1H, 3J(H–H) = 8.0, 4J(H–H) = 1.9, H2), 4.07 (q,
1H, 3J(H–H) = 7.2, H5), 3.43 (s, 3H, CO2Me), 0.94 (d, 3H, 3J(H–
H) = 7.2, H6), 0.78 (d, 3H, 2J(Pt–H) = 82.4, J(P–H) = 7.5, Me).
31P{1H} NMR (121.4 MHz) d: 30.34 (s, 1J(Pt–P) = 2268.4). 195Pt
[PtMe2I{j
2-(C,N)-4-ClC6H3CH@NCH2CO2Me}(PPh3)] (4a). An ex-
cess (0.15 mL, 2.4 mmol) of methyl iodide was added to a solution
of 3a (75 mg, 0.11 mmol) in acetone. The solution was stirred at
room temperature for 2 h and the solvent was concentrated to dry-
ness on a rotatory evaporator. After addition of diethyl ether to the
residue a white solid was obtained. The solid was washed with
diethyl ether and dried to obtain 4a. Yield: 68 mg (76%). 1H NMR
NMR (53.8 MHz) d: ꢁ4234.3 (d, 1J(Pt–P) = 2284.8). IR (KBr),
m
(cmꢁ1):
t
(C@O) = 1737,
t(C@N) = 1622, PPh3 (q-X sensi-
tive) = 1096. MS-MALDI TOF (+) m/z: [M+H]+ = 695.8, [MꢁMe]+ =
681.8. Anal. Calc. for C30H29ClNO2PPt: C, 51.69; H, 4.19; N, 2.01.
Found: C, 51.8; H, 4.4; N, 2.0%.