2230
P. Chellan et al. / Journal of Organometallic Chemistry 695 (2010) 2225e2232
d
(ppm) ¼ 176.9 (CeS), 168.2 (C]N), 164.1 (C1), 151.5 (C6), 136.5
(C4), 133.9e128.6 (C3 and PPh3), 126.3 (C5), 125.9 (C2), 19.5 (CH2),
10.9 (CH3). 31P NMR (121.47 MHz, DMSO):
(ppm) ¼ 38.55 (PPh3).
IR (KBr, cmꢀ1
4.9. Synthesis of [Pd2(3,4-dichloropropiophenone
thiosemicarbazone)2(trans-dppe)] (10)
d
)
y
¼ 3466 (m, NeH), 3289 (s, NeH), 1618 (s, C]N),
Bis(diphenylphosphinoethylene) (0.0460 g, 0.116 mmol) was
reacted with compound 4 (0.0884 g, 0.0581 mmol). The product
1577 (m, C]N), 1481 (s, C]C aromatics). Elemental Analysis for
C28H24Cl2N3PPdS: found C 52.2, H 3.9, N 5.9, S 4.6%; calculated C
52.3, H 3.8, N 6.5, S 5.0%. ESI-MS: m/z 644 ([M þ H]þ, 100%).
was isolated as
a yellow solid. Yield: 0.0615 g, 91%. M.p.:
216e218 ꢁC (decomp.). 1H NMR (399.95 MHz, DMSO):
d
(ppm) ¼ 7.52e7.58 (m, 20H, PPh2), 7.17e7.26 (m, 4H, H2,
4.6. Synthesis of [Pd2(3,4-dichloroacetophenone
thiosemicarbazone)2(dppf)] (7)
PPh2CH]CHPPh2), 6.99 (s, 4H, NH2), 6.22 (s, 2H, H5), 2.77 (q,
J ¼ 7.24, 7.23 Hz, 4H, CH2), 1.13 (t, J ¼ 7.50 Hz, 6H, CH3). 13C NMR
(100.57 MHz, DMSO):
d
(ppm) ¼ 176.6 (CeS), 168.4 (C]N), 163.7
Bis(diphenylphosphinoferrocene) (0.0786 g, 0.142 mmol) was
reacted with compound 3 (0.105 g, 0.0717 mmol). The product was
isolated as a yellow solid. Yield: 0.127 g, 90%. M.p.: decomposition
without melting 204e206 ꢁC. 1H NMR (399.95 MHz, DMSO):
(C1), 151.3 (C6), 140.9 (C4), 135.8 (C3), 132.9e133.2 (PPh2), 131.4
(PPh2CH]CHPPh23)1, 128.6e128.9 (PPh2), 126.5 (C5), 125.9 (C2), 19.6
(CH2), 10.8 (CH3). P NMR (161.90 MHz, DMSO):
d
(ppm) ¼ 33.71
(PPh2). IR (KBr, cmꢀ1
)
y
¼ 3496 (m, NeH), 3386 (s, NeH), 1594 (s,
d
(ppm) ¼ 7.40e7.58 (m, 20H, PPh2), 7.25 (s, 2H, H2), 6.96 (s, 4H,
NH2), 6.08 (s, 2H, H5), 5.07 (br, 4H, Cp-H), 4.27 (br, 4H, Cp-H), 2.31
(s, 6H, CH3). 13C NMR (100.57 MHz, DMSO):
C]N), 1573 (m, C]N), 1486 (s, C]C aromatics). Elemental Analysis
for C46H40Cl4N6P2Pd2S2: found C 47.2, H 3.6, N 7.9, S 5.7%; calculated
C 47.8, H 3.5, N 7.3, S 5.5%. ESI-MS: m/z 1158.91 ([M þ H]þ, 25%),
579.96 ([M/2 þ 2H]2þ, 100%).
d
(ppm) ¼ 178.6 (CeS),
163.8 (C]N), 152.7 (C1), 136.14 (C6), 133.0e133.2 (PPh2), 131.1 (C4),
129.4 (C3), 128.4e128.5 (PPh2), 126.4 (C5), 126.3 (C2), 75.4e74.2
(Cp), 13.3 (CH3). 31P NMR (161.90 MHz, DMSO):
d
(ppm) ¼ 29.19
4.10. Synthesis of [Pd2(3,4-dichloroacetophenone
thiosemicarbazone)2(dppb)] (11)
(PPh3). IR (KBr, cmꢀ1
)
y
¼ 3479 (m, NeH), 3383 (m, NeH), 1595 (s,
C]N), 1574 (s, C]N), 1491 (s, C]C aromatics). Elemental Analysis
for C52H42Cl4FeN6P2Pd2S2: found C 49.0, H 3.5, N 6.2, S 4.1%;
calculated C 48.5, H 3.3, N 6.5, S 5.0%. ESI-MS: m/z 1288.87
([M þ H]þ, 50%), 644.94 ([M/2 þ 2H]2þ, 100%).
Bis(diphenylphosphinobenzene) (0.0631 g, 0.149 mmol) was
reacted with compound 3 (0.0947 g, 0.0646 mmol). The product
was isolated as a yellow solid. Yield: 0.0686 g, 90%. M.p.:
142e143 ꢁC (decomp.). 1H NMR (300.07 MHz, DMSO):
4.7. Synthesis of [Pd2(3,4-dichloropropiophenone
thiosemicarbazone)2(dppf)] (8)
d
(ppm) ¼ 7.48e7.76 (m, 24H, PPh2, PeC6H4eP), 7.23 (s, 2H, H2),
6.95 (s, 4H, NH2), 6.08 (s, 2H, H5), 2.27 (s, 6H, CH3). 13C NMR
(100.57 MHz, DMSO):
d
(ppm) ¼ 165.1 (CeS), 163.9 (C]N), 153.2
Bis(diphenylphosphinoferrocene) (0.0518 g, 0.0934 mmol) was
reacted with compound 4 (0.0713 g, 0.0468 mmol). The product
was isolated as a yellow solid. Yield: 0.0552 g, 89%. M.p.: decom-
position without melting 196e198 ꢁC. 1H NMR (399.95 MHz,
(C1), 136.8 (C6), 128.8e134.7 (PPh2, PeC6H4eP, C3, C4), 126.7 (C5),
126.3 (C2), 13.8 (CH3). 31P NMR (161.90 MHz, DMSO):
d
(ppm) ¼ 38.96 (PPh2). IR (KBr, cmꢀ1
)
y
¼ 3396 (m, NeH), 3055 (m,
NeH), 1610 (s, C]N), 1561 (s, C]N), 1482 (s, C]C aromatics), 1436
(C]C, aromatics). Elemental Analysis for C48H38Cl4N6P2Pd2S2:
found C 48.3, H 3.2, N 7.1, S 5.5%; calculated C 48.9, H 3.2, N 7.1, S
DMSO):
d
(ppm) ¼ 7.45e7.56 (m, 20H, PPh2), 7.26 (s, 2H, H2), 6.98
(s, 4H, NH2), 6.10 (s, 2H, H5), 5.03 (br, 4H, Cp-H), 4.27 (br, 4H, Cp-H),
2.79 (q, J ¼ 7.00, 6.92 Hz, 2H, CH2), 1.11 (t, J ¼ 7.46 Hz, 6H, CH3). 13
C
5.4%. ESI-MS: m/z 1180.89 ([M þ H]þ, 30%), 590.95 ([M/2 þ 2H]2þ
,
NMR (100.57 MHz, DMSO):
d
(ppm) ¼ 176.8 (CeS), 168.3 (C]N),
100%).
151.4 (C1), 136.2 (C6), 133.1e132.9 (PPh2), 130.8 (Cd), 129.3 (Cc),
128.3e128.2 (PPh2), 126.4 (Ce), 125.8 (Cb), 74.6e75.1 (Cp), 19.6
4.11. Synthesis of [Pd2(3,4-dichloropropiophenone
thiosemicarbazone)2(dppb)] (12)
(CH2), 10.8 (CH3). 31P NMR (161.90 MHz, DMSO):
d
(ppm) ¼ 29.12
(PPh2). IR (KBr, cmꢀ1
) y
¼ 3467 (m, NeH), 3387 (m, NeH), 1591 (s,
C]N), 1567 (m, C]N), 1491 (s, C]C aromatics). Elemental Analysis
for C54H46Cl4FeN6P2Pd2S2: found C 49.0, H 3.5, N 6.9, S 4.3%;
calculated C 49.3, H 3.5, N 6.4, S 4.9%. ESI-MS: m/z 1316.89
([M þ H]þ, 50%), 658.95 ([M/2 þ 2H]2þ, 100%).
Bis(diphenylphosphinobenzene) (0.0562 g, 0.133 mmol) was
reacted with compound 4 (0.0967 g, 0.0635 mmol). The product
was isolated as a yellow solid. Yield: 0.0727 g, 95%. M.p.:
268e270 ꢁC (decomp.). 1H NMR (300.07 MHz, DMSO):
d
(ppm) ¼ 7.71e7.75 (m, 4H, PeC6H4eP), 7.48e7.51 (m, 20H, PPh2),
4.8. Synthesis of [Pd2(3,4-dichloroacetophenone
thiosemicarbazone)2(trans-dppe)] (9)
7.21 (s, 2H, H2), 6.84 (s, 4H, NH2), 6.10 (s, 2H, H5), 2.73 (q, J ¼ 7.43,
7.34 Hz, 4H, CH2), 1.09(t, J ¼ 7.40 Hz, 6H, CH3). 13C NMR
(100.57 MHz, DMSO):
d
(ppm) ¼ 177.4 (CeS), 169.1 (C]N), 164.7
Bis(diphenylphosphinoethylene) (0.0592 g, 0.149 mmol) was
reacted with compound 3 (0.105 g, 0.0719 mmol). The product was
isolated as a yellow solid. Yield: 0.134 g, 79%. M.p.: 211e213 ꢁC
(C1), 152.1 (C6), 137.0 (C4), 134.4e134.6 (PPh2), 131.9 (PPh2CH]
CHPPh2), 130.8 (C3), 129.3e129.4 (PPh2), 127.1 (C5), 126.6 (C2), 20.2
(CH2), 11.48 (CH3). 31P NMR (161.90 MHz, DMSO):
d
(ppm) ¼ 38.80
(decomp.). 1H NMR (399.95 MHz, DMSO):
d
(ppm) ¼ 7.52e7.57 (m,
(PPh2). IR (KBr, cmꢀ1
) y
¼ 3511 (m, NeH), 3403 (s, NeH), 1617 (m,
20H, PPh2), 7.28e7.33 (m, 2H, PPh2CH]CHPPh2), 7.21 (s, 2H, H2),
C]N), 1591 (s, C]N), 1525 (C]C, aromatics), 1482 (s, C]C
aromatics). Elemental Analysis for C50H42Cl4N6P2Pd2S2: found C
49.3, H 3.6, N 4.8, S 5.4%; calculated C 49.7, H 3.5, N 5.0, S 5.3%. ESI-
MS: m/z 1206.94 ([M þ H]þ, 50%), 604.97 ([M/2 þ 2H]2þ, 100%).
6.95 (s, 4H, NH2), 6.23 (s, 2H, H5), 2.28 (s, 6H, CH3). 13C NMR
(100.57 MHz, DMSO):
d
(ppm) ¼ 176.6 (CeS), 164.0 (C]N), 163.3
(C1), 152.6 (C6), 135.7 (C4), 133.1e133.2 (PPh2), 131.4 (PPh2CH]
CHPPh2), 131.1 (C3), 128.9e129.0 (PPh2), 126.6 (C5), 125.3 (C2), 13.1
(CH3). 31P NMR (161.90 MHz, DMSO):
d
(ppm) ¼ 34.18 (PPh2). IR
4.12. X-ray crystallography
(KBr, cmꢀ1
)
y
¼ 3455 (m, NeH), 3317 (s, NeH), 1623 (m, C]N), 1605
(s, C]N), 1483 (s, C]C aromatics). Elemental Analysis for
C44H36Cl4N6P2Pd2S2: found C 46.8, H 3.2, N 7.3, S 5.7%; calculated C
46.8, H 3.2, N 7.4, S 5.7%. ESI-MS: m/z 1130.88 ([M þ H]þ, 50%),
565.95 ([M/2 þ 2H]2þ, 100%).
For complex 6, X-ray single crystal intensity data were collected
on a Nonius Kappa-CCD diffractometer using graphite mono-
chromated MoK
Oxford Cryostream cooling system (Oxford Cryostat). The strategy
a radiation. Temperature was controlled by an