ꢀ
ꢀ
ꢀ
P. Stepnicka et al. / Journal of Organometallic Chemistry 696 (2011) 3727e3740
3737
w, 693 s, 624 m, 593 w, 567 w, 547 m, 518 s, 503 m, 483 m, 467 m,
455 m, 438 m cmꢀ1. Anal. calc. for C46H42Cl2Fe2N4O2P2Pd$1.2CHCl3
(1177.0): C 48.16, H 3.76, N 4.76%; found: C 47.99, H 3.77, N 4.60%.
Note: The complex is insoluble in common deuterated solvents.
dichloromethane. Isolation as above afforded 11 as an orange solid.
Yield: 19.6 mg (27%; the compound is highly soluble).
4
1H NMR (CDCl3):
d
2.89 (d, JPH ¼ 2.8 Hz, 6 H, NCH3), 4.16 (d,
4JPH ¼ 2.4 Hz, 2 H, NCH2), 4.29e4.30 (m, 2 H, fc), 4.48 (vq, J0 ¼ 2.0 Hz,
2 H, fc), 5.04 (vt, J0 ¼ 2.0 Hz, 2 H, fc), 5.12 (vt, J0 ¼ 1.9 Hz, 2 H, fc),
6.22e6.26 (m, 1 H, C6H4), 6.39 (dt, JHH ¼ 7.5, 1.2 Hz, 1 H, C6H4), 6.84
(dt, JHH ¼ 7.3, 1.1 Hz, 1 H, C6H4), 7.03 (dd, JHH ¼ 7.0, 1.5 Hz, 1 H, C6H4),
7.30e7.36 (m, 4 H, Ph), 7.38e7.45 (m, 2 H, Ph), 7.51e7.58 (m, 4 H,
4.10. Synthesis of [SP-4-4]-chlorido{[(2-dimethylamino-
phenyl- P)-1-carbamoylferrocene]
C1}[10-(diphenylphosphino-
palladium(II) (9)
kN)methyl]
k
k
Ph), 8.32 (s, 1 H, CH oxadiazole) ppm. 31P{1H} NMR (CDCl3):
d
þ32.5
(s) ppm. ESI þ MS: m/z 678 [MeCl]þ. IR (Nujol): 1591 s, 1516 m,
1436 m, 1306 m, 1266 w, 1182 w, 1164 s, 1122 w, 1097 s, 1029 s,
993 m, 971 w, 954 m, 864 w, 844 s, 739 s, 695 s, 641 m, 629 m, 568
w, 544 s, 509 s, 478 m, 434 m cmꢀ1. Anal. calc. for C33H31ClFe-
N3OPPd (714.3): C 55.49, H 4.37, N 5.88%; found C 55.67, H 4.56, N
5.60%.
[(LNC)PdCl]2 (27.6 mg, 0.05 mmol) and 1,½AcOEt (45.7 mg,
0.10 mmol) were dissolved in dichloromethane (10 mL). The
resulting solution was stirred 30 min and then precipitated with
pentane. After standing at 4 ꢁC overnight, the separated solid was
filtered off, washed with pentane and dried under vacuum to give
9$½CH2Cl2. Yield: 68.5 mg (94%), fine orange solid.
4
1H NMR (CDCl3):
d
2.86 (d, JPH ¼ 2.4 Hz, 6 H, NCH3), 4.13 (d,
4JPH ¼ 1.7 Hz, 2 H, NCH2), 4.45e4.49 (m, 4 H), 4.70 (vt, J0 ¼ 2.0 Hz,
2 H) and 5.04 (vt, J0 ¼ 2.0 Hz, 2 H) (4 ꢂ CH of fc); 5.32 (s,1 H, CH2Cl2),
5.37 (br s, 1 H, NH2), 6.23e6.28 (m, 1 H, C6H4), 6.37 (dt, JHH ¼ 7.7,
1.6 Hz, 1 H, C6H4), 6.60 (s, 1 H, NH2), 6.81 (dt, JHH ¼ 7.3, 1.1 Hz, 1 H,
C6H4), 7.00 (dd, JHH ¼ 7.5, 1.6 Hz, 1 H, C6H4), 7.29e7.35 (m, 4 H, Ph),
7.37e7.43 (m, 2 H, Ph), 7.54e7.61(m, 4 H, Ph) ppm. 31P{1H} NMR
4.13. Synthesis of [SP-4-4]-chlorido{[(2-dimethylamino-
kN)methyl]
phenyl- P)ferrocene-1-carbonyl]-
k
C1}{1-[10-(diphenylphosphino-
k
3,5-dimethyl-1,2-pyrazole}palladium(II) (12)
Pyrazole 5 (24.6 mg, 0.05 mmol) and [(LNC)PdCl]2 (13.8 mg,
0.025 mmol) were dissolved in dichloromethane (3 mL). The
mixture was stirred for 30 min and then evaporated under vacuum.
The residue was washed with pentane and dried under vacuum to
give 12 as a non-stoichiometric solvate 12,0.67C5H12. Yield:
39.8 mg (97%), an orange amorphous solid.
(CDCl3):
d
þ32.4 (s) ppm. ESI þ MS: m/z 653 [MeCl]þ. IR (Nujol):
1655 s, 1604 s, 1164 m, 1099 m, 1028 m, 844 m, 743 s, 695 m, 505 w
cmꢀ1. Anal. calc. for C32H32ClFeN2OPPd$½CH2Cl2 (731.7): C 53.34, H
4.55, N 3.83%; found C 53.42, 4.57, 3.64%.
1H NMR (CDCl3):
d
0.85e0.91 and 1.22e1.34 (2 ꢂ m, pentane);
2.18 (s, 3 H) and 2.54 (d, 4JHH z 1 Hz, 3 H) (2 ꢂ CH3 pyrazole); 2.87
4.11. Synthesis of [SP-4-3]-{[(2-dimethylamino-
C1}[10-(diphenylphosphino-
P)-1-(carbamoyl-
palladium(II) hexafluoroantimonate (10)
k
N)methyl]phenyl-
4
4
(d, JPH ¼ 2.7 Hz, 6 H, NCH3), 4.16 (d, JPH ¼ 2.2 Hz, 2 H, NCH2),
4.36e4.38 (m, 2 H, fc), 4.46 (vq, J0 ¼ 1.9 Hz, 2 H, fc), 5.07 (vt,
J0 ¼ 2.0 Hz, 2 H, fc), 5.50 (vt, J0 ¼ 2.0 Hz, 2 H, fc), 5.96 (d, J z 1 Hz,1 H,
CH pyrazole), 6.22e6.26 (m, 1 H, C6H4), 6.39 (dt, JHH ¼ 7.4, 1.2 Hz,
1 H, C6H4), 6.83 (dt, 4JHH ¼ 7.4, 1.2 Hz, 1 H, C6H4), 7.02 (dd, JHH ¼ 7.4,
1.6 Hz, 1 H, C6H4), 7.27e7.33 (m, 4 H, Ph), 7.37e7.43 (m, 2 H, Ph),
k
k
kO)ferrocene]
Solid [(LNC)PdCl]2 (27.6 mg, 0.05 mmol) and 1,½AcOEt (45.7 mg,
0.10 mmol) were dissolved in MeCN (8 mL). After stirring the
mixture for 30 min, a solution of Ag[SbF6] (34.4 mg, 0.10 mmol) in
MeCN (2 mL) was introduced causing immediate separation of an
off-white solid (AgCl). The reaction mixture was stirred for another
7.50e7.59 (m, 4 H, Ph) ppm. 31P{1H} NMR (CDCl3):
d
þ32.6 (s) ppm.
ESI þ MS: m/z 732 [MeCl]þ. IR (Nujol): 3100 w, 3049 w, 1681 s,
1580 m, 1437 w, 1409 w, 1338 s, 1283 m, 1223 w, 1165 m, 1099 m,
1045 m, 993 w, 967 m, 845 s, 769 w, 745 s, 695 s, 629 m, 543 m,
30 min in the dark and then filtered trough a 0.45 mm PTFE syringe
505 s, 476 m, 440
w . Anal. calc. for C37H37ClFe-
cmꢀ1
filter. The filtrate was evaporated and the crude product was
crystallized from dichloromethaneehexane by liquid phase diffu-
sion. The separated crystals were isolated by suction, washed
successively with diethyl ether and pentane, and dried under
vacuum to afford 10 as red-orange crystalline solid. Yield: 64 mg
N3OPPd$0.67C5H12 (816.7): C 59.33, H 5.56, N 5.15%, found C 59.23,
H 4.52, N 4.83%.
4.14. Synthesis of [SP-4-3]-{[(2-dimethylamino-
C1}{1-[10-(diphenylphosphino-
P)ferrocene-1-carbonyl]-3,5-
dimethyl-1,2-pyrazole-
N1}palladium(II) hexafluoroantimonate (13)
kN)methyl]phenyl-
(72%).
k
k
4
1H NMR (CD2Cl2):
d
2.77 (d, JPH ¼ 3 Hz, 6 H, NCH3), 4.11 (vq,
k
J0 ¼ 1.6 Hz, 2 H, fc), 4.13 (d, 4JPH ¼ 2.2 Hz, 2 H, NCH2), 4.65e4.68 (m,
4 H, fc), 5.38 (vt, J0 ¼ 2.0 Hz, 2 H, fc), 6.12 (s, 1 H, NH2), 6.27 (dt,
JHH ¼ 6.6, 1.2 Hz, 1 H, C6H4), 6.35e6.41 (m, 1 H, C6H4), 6.63 (s, 1 H,
NH2), 6.86 (dt, JHH ¼ 7.3, 1.1 Hz, 1 H, C6H4), 7.00e7.03 (m, 1 H, C6H4),
7.38e7.44 (m, 4 H, Ph), 7.47e7.52 (m, 2 H, Ph), 7.70e7.76 (m, 4 H,
A
suspension of Ag[SbF6] in dichloromethane (17.2 mg,
0.05 mmol in 1 mL) was added to a solution of complex 12, which
was generated in situ by stirring a mixture of pyrazole 5 (24.6 mg,
0.05 mmol) and [(LNC)PdCl]2 (13.8 mg, 0.025 mmol) in dichloro-
methane (3 mL) for 30 min. After stirring for another 30 min, the
AgCl formed was filtered off and the filtrate was evaporated. The
residue was washed with pentane and dried under vacuum to
afford 13 as a red solid. Yield: 47.9 mg (quantitative).
Ph) ppm. 31P{1H} NMR (CDCl3):
d
þ29.9 (s) ppm. ESI þ MS: m/z 653
([LNCPd(1)]þ). IR (Nujol): 3414 m, 3338 m, 3280e3160 m, 3120 w,
3093 w, 3043 w, 1655 s, 1568 s, 1437 w, 1393 w, 1337 w, 1306 m,
1186 m, 1169 s, 1099 s, 1073 w, 1047 m, 1025 s, 997 m, 977 w, 916 w,
892 w, 856 s, 843 m, 818 s, 770 m, 750 s, 738 s, 695 s, 664 s, 643 s,
1H NMR (50 ꢁC, CDCl3):
d
1.90 (s, 3 H) and 2.43 (d, JPH ¼ 2.4 Hz,
616 w, 564 m, 539 s, 522 s, 507 s, 484 m, 472 w, 457 w, 442 s cmꢀ1
.
3 H) (2 ꢂ CH3 pyrazole), 2.58 (d, 4JPH ¼ 2.8 Hz, 6 H, NCH3), 4.16 (s,
2 H, NCH2), 4.58 (s, 2 H, fc), 4.76 (s, 2 H, fc), 5.12 (s, 4 H, fc), 6.06 (s,
1 H, CH pyrazole), 6.20e6.24 (m, 1 H, C6H4), 6.34e6.38 (m, 1 H,
C6H4), 6.84 (dt, JHH ¼ 7.4,1.1 Hz,1 H, C6H4), 7.01 (dd, JHH ¼ 7.4,1.6 Hz,
1 H, C6H4), 7.22e7.40 (m, 10 H, Ph) ppm. 31P{1H} NMR (CDCl3):
Anal. calc. for C32H32F6FeN2OPPdSb (889.6): C 43.20, H 3.63, N
3.15%; found C 43.08, H 3.62, N 3.05%.
4.12. Synthesis of [SP-4-4]-chlorido{[(2-dimethylamino-
phenyl- P)-1-(1,3,4-oxadiazol-2-yl)
C1}[10-(diphenylphosphino-
ferrocene]palladium(II) (11)
kN)methyl]
k
k
d
þ25.7 (s) ppm. ESI þ MS: m/z 732 [LNCPd(5)]þ. IR (Nujol): 3120 w,
3050 w, 1688 s, 1561 m, 1342 m, 1292 s, 1209 w, 1164 m, 1096 m,
1045 w, 997 w, 843 m, 752 s, 696 m, 659 s, 525 m, 489 m cmꢀ1. Anal.
calc. for C37H37F6FeN3OPPdSb (968.7): C 45.87, H 3.85, N 4.34%;
found C 46.13, H 4.09, N 4.06%.
Complex 11 was prepared similarly to 9 from [(LNC)PdCl]2
(27.6 mg, 0.05 mmol) and 4 (43.8 mg, 0.10 mmol) in 5 mL of