Palladium(II) Complexes with Aminomethylphosphine Ligands
5
Yield 0.15 g (65%), mp: 190–192◦C. 1H NMR (CDCl3,
25◦C, ppm): δ 7.6–6.6 (m, 29H, Ph), 4.4 (d, 4H, P-CH2-
N). 13C NMR (400 MHz, CDCl3, ppm): δ 148.9–117.9
(Ar-C), 56.3 (N-CH2-P). 31P NMR (CDCl3, 25◦C, ppm):
δ 9.8 (Pd-PPh2). Anal. Calcd. for C38H33Cl2NSP2Pd: C,
58.90; H, 4.30; N, 1.80. Found: C, 58.40; H, 4.12; N,
1.63.
(0.4 g, 2 mmol) in toluene (10 mL). Yield 0.82 g
1
(71%). H NMR (CDCl3, 25◦C, ppm): δ 7.3–6.7 (m,
29H, Ph), 4.0 (d, 4H, P-CH2-N). 13C NMR (400 MHz,
CDCl3, ppm): δ 134.0–128.6 (Ar-C), 59.7 (N-CH2-P).
31P NMR (CDCl3, 25◦C, ppm): δ –26.4 (PPh2). Anal.
Calcd. for C38H33NOP2: C, 78.47; H, 5.72; N, 2.41.
Found: C, 77.92; H, 5.10; N, 2.62.
Preparation of (((C6H5)2PCH2)2NC6H4SC6H5)
(1c). Ligand 1c was prepared in the same way as
1a from Ph2PH (0.72 mL, 3.8 mmol) HCHO (0.4
mL, 7 mmol), and 2-(phenylthio)aniline (0.4 g, 1.9
mmol) in toluene (10 mL). Yield 0.93 g, (78%).1H
NMR (CDCl3, 25◦C, ppm): δ 7.3–6.7 (m, 29H, Ph),
3.9 (d, 4H, P-CH2-N) 13C NMR (400 MHz, CDCl3,
ppm): δ 138.4–129.2 (Ar-C), 58.0 (N-CH2-P). 31P
NMR (CDCl3, 25◦C, ppm): δ –27.5 ( PPh2). Anal.
Calcd. for C38H33NSP2: C, 76.36; H, 5.57; N, 2.34.
Found: C, 76.72; H, 5.60; N, 2.32.
General Procedure for Heck Reactions
An oven-dried Schlenk flask was charged with
NEt3 (1.2 mmol) and NMP (2 mL) under
nitrogenatmosphere followed by aryl halide (1
mmol), olefin (1.2 mmol), and Pd(II) catalyst (1%
mol). The flask was then sealed under N2 atmosphere
and placed in an oil bath preheated at 120◦C. The
reaction mixture was stirred and then allowed to
cool to room temperature. The reaction mixture was
poured into water (20 mL) and extracted with ethyl
acetate (3×20 mL). The extracts were washed with
brine and dried over MgSO4, and solvent was evap-
orated.
Preparation of [PdCl2 ((Ph2 PCH2)2 NC6 H5 (CH3)
(OH)](2a). 1a (0.36 g, 0.70 mmol) was added to a
stirred solution of [PdCl2(cod)] (0.10 g, 0.35 mmol)
in CH2Cl2 (10 mL). The mixture was refluxed for 3 h.
At the end of the reaction, addition of diethylether
gave a yellow solid, which was filtered off and dried.
Yield 0.17 g (80%), mp: 158–159◦C. 1H NMR (CDCl3,
25◦C, ppm): δ 7.9–7.3 (m, 23H, Ph], 4.1 (d, 4H, P-
CH2-N), 2.2 ( CH3), 5.4 (br, OH). 13C NMR (400
MHz, CDCl3, ppm): δ 134.1–121.8 (Ar-C), 56.0 (N-
CH2-P), 21.4 (C-CH3). 31P NMR (CDCl3, 25◦C, ppm):
δ 7.8 (Pd-PPh2). Anal. Calcd. for C33H31Cl2NOP2Pd:
C, 56.90; H, 4.50; N, 2.01. Found: C, 56.72; H, 4.10;
N, 1.94.
CONCLUSIONS
Pd(II) complexes with aminomethyldiphosphine
(P C N) ligands have been synthesized and charac-
terized using spectroscopic techniques. The 31P{ H}
1
NMR spectra of the complexes indicate that coordi-
nation of the aminomethylphosphine ligand occurs
via two phosphorus atoms. The complexes have been
tested as catalysts for the Heck reaction. The results
showed that all the complex 2a–2c catalyzed the re-
action of olefin with aryl halide in excellent yields.
Preparation of [PdCl2 (((C6 H5)2 PCH2)2 N C6 H4O
C6H5)] (2b). 1b (0.29 g, 0.50 mmol) was added to a
stirred solution of [PdCl2(cod)] (0.08 g, 0.25 mmol)
in CH2Cl2 (10 mL). The mixture was refluxed for 3 h.
At the end of the reaction, addition of diethylether
gave a pale yellow solid, which was filtered off and
ACKNOWLEDGMENTS
We thank Osmaniye Korkut Ata University for finan-
cial support. We are also grateful to the Department
of Chemistry at Inonu University for the use of the
NMR facility and elemental analyses.
1
dried. Yield 0.15 g (78%), mp: 248–250◦C. H NMR
(CDCl3, 25◦C, ppm): δ 7.9–6.6 (m, 29H, Ph), 3.9 (d,
4H, P-CH2-N). 13C NMR (400 MHz, CDCl3, ppm):
δ 134.3–118.938 (Ar-C), 56.4 (N-CH2-P). 31P NMR
(CDCl3, 25◦C, ppm): δ 9.6 (Pd-PPh2). Anal. Calcd. for
C38H33Cl2NOP2Pd: C, 60.10; H, 4.40; N, 1.85. Found:
C, 59.68; H, 4.20; N, 1.74.
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Preparation of [PdCl2 ( ( ( C6H5)2 PCH2)2 N C6 H4 S
C6H5)] (2c). 1c (0.36 g, 0.60 mmol) was added to a
stirred solution of [PdCl2(cod)] (0.096 g, 0.30 mmol)
in CH2Cl2 (10 mL). The mixture was refluxed for 4 h.
At the end of the reaction, addition of diethylether
gave a yellow solid, which was filtered off and dried.
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Heteroatom Chemistry DOI 10.1002/hc