1
324
C. Xi et al. / Polyhedron 52 (2013) 1323–1328
Structure solution and refinement were performed by using the
HELXL-97 package [10].
Table 1
Comparison of NMR data for ligand L1–L3 and complex C1–C6.
S
L1
L2
L3
C1
C2
C3
C4
C5
C6
2
.2. General procedure for the synthesis of the dipalladium complexes
d
d
C=CH
6.57
9.1
6.57
9.0
6.60
27.4
8.03
44.0
8.00
43.2
7.62
65.2
7.93
35.6
7.90
36.5
7.39
44.3
C1–C3
P
Dipalladium complexes C1–C3 were synthesized by the follow-
ing general procedure. PdCl (CH CN) (0.10 mmol) and (E)-(1,2-
2
3
2
d 1.33 (m, 24H), 2.46 (m, 4H); 5.28 (s, 1H), 7.00–7.53 (m, aromatic,
diarylvinyl)diphenylphosphine as ligand (0.10 mmol) were mixed
in dichloromethane. The mixture was stirred at room temperature
for 12 h, giving an orange suspension. The reaction volume was re-
duced, diethyl ether was added, and orange solids were obtained,
which were washed repeatedly with diethyl ether and dried under
vacuum. The red powder was obtained.
13
2
1
1
3 4
0H), 7.62 (d, 2H JPH = 19.9 Hz); C NMR (75 MHz, CDCl , Me Si) d
8.4, 18.5, 18.6,19.6, 19.9, 26.0 (d, JPC = 28.7 Hz), 53.5, 126.6, 127.2,
27.7, 128.3, 128.5, 128.8, 128.9, 129.2, 129.4, 130.4, 136.0 (d,
31
JPC = 19.6 Hz), 137.4, 147.9 (d, JPC = 12.9 Hz); P NMR (81 MHz,
À1
CDCl
3
, 85%H
3
PO
4
) d 65.2. IR (KBr; cm ): 2954, 2924, 2855, 2361,
2
C
5
337, 1461, 1094, 810, 733, 695. Anal. Calc. for
40
H50Cl
4 2
P
Pd Cl : C, 49.14; H, 5.19. Found: C, 48.92; H,
2
Á0.5CH
2
2
2
.2.1. Complex C1
PdCl (CH CN)
nyl)diphenylphosphine L1 (0.10 mmol, 36 mg). Yield: 89%
.03%.
2
3
2
(0.10 mmol, 26 mg) and (E)-(1,2-diphenylvi-
1
2.3. General procedure for the synthesis of the monopalladium
complexes C4–C6
(
6
48 mg). Mp: 159–162 °C. H NMR (300 MHz, CDCl3, Me
.96–7.74 (m, aromatic, 40H), 8.03 (d, 2H, JPH = 23.3 Hz);
NMR (75 MHz, CDCl , Me Si) d 126.5, 127.2, 128.1, 128.3, 128.4,
28.9, 129.4, 130.1, 130.5, 130.8 (d, JPC = 48.2 Hz), 131.7, 135.0 (d,
4
Si) d
1
3
C
3
4
Complexes C4–C6 were synthesized by the following general
1
J
3
1
procedure. PdCl
2
(CH
3
CN)
2
(0.10 mmol) and (E)-(1,2-diarylvi-
PC = 20.8 Hz), 135.6 (d, JPC = 10.8 Hz), 148.7 (d, JPC = 14.3 Hz);
P
À1
nyl)diphenylphosphine as ligand (0.22 mmol) were mixed in
dichloromethane. The mixture was stirred at room temperature
for 12 h, giving an orange suspension. The reaction volume was re-
duced, diethyl ether was added, and yellow solids were obtained,
which were washed repeatedly with diethyl ether and dried under
vacuum. The yellow powder was obtained.
NMR (81 MHz, CDCl
3
, 85% H
3
PO
4
) d 44.0. IR (KBr; cm ): 2953,
2
9
3
920, 2848, 2678, 2330, 1961, 1607, 1485, 1435, 1266, 1093,
45, 744, 731. Anal. Calc. for C52
H42Cl
4
2
P Pd
2 3
Á2CHCl : C, 49.05; H,
.35. Found: C, 49.14; H, 3.31%.
2
.2.2. Complex C2
PdCl (CH CN)
nyl)diphenylphosphine L2 (0.10 mmol, 39 mg). Yield: 95%
2
3
2
(0.10 mmol, 26 mg) and (E)-(1,2-ditolylvi-
2.3.1. Complex C4
1
PdCl (CH CN) (0.10 mmol, 26 mg) and (E)-(1,2-diphenylvi-
(
54 mg). Mp: 183–185 °C. H NMR (300 MHz, CDCl3, Me
4
Si) d
2
3
2
nyl)diphenylphosphine L1 (0.22 mmol, 80 mg). Yield: 93%
2
.25 (s, 12H); 6.91–7.73 (m, aromatic, 36H), 8.00 (d, 2H,
1
1
3
4
(84 mg) Mp: 225–230 °C. H NMR (300 MHz, CDCl3, Me Si) d
JPH = 23.7 Hz); C NMR (75 MHz, CDCl
3 4
, Me Si) d 21.4, 125.4,
7
(
1
.03–7.74 (m, aromatic, 40H), 7.93 (t, 2H, JPH = 10.5 Hz); 13C NMR
75 MHz, CDCl , Me Si) d 127.4, 127.7, 127.8, 128.2, 128.6, 128.9,
29.2, 129.5, 129.9, 130.2, 130.5, 132.5, 132.8, 133.0, 135.6,
1
1
1
26.2, 127.7, 128.1, 128.3, 128.4, 128.6, 129.1, 129.2, 129.6,
29.9, 130.0, 130.5, 130.8, 131.0, 131.6, 132.2, 132.4, 132.7,
33.6, 133.8, 135.5, 135.3, 135.6, 137.8138.3, 139.5139.9, 148.8
3
4
31
31
135.7, 135.8, 146.5 (d, JPC = 11.5 Hz), 146.7 (d, JPC = 11.5 Hz);
NMR (81 MHz, CDCl , 85% H PO ) d 35.6. IR (KBr; cm ): 3049,
P
(
3
d, JPC = 18.6 Hz), 149.0 (d, JPC = 17.9 Hz); P NMR (81 MHz, CDCl ,
À1
À1
8
2
9
4
5% H
3
PO
4
) d 43.2. IR (KBr; cm ): 3072, 3050, 3017, 2918, 2861,
3
3
4
3
1
4
017, 2918, 2858, 2730, 2360, 2336, 1604, 1506, 1432, 1283,
361, 1604, 1567, 1505, 1479, 1431, 1309, 1183, 1093, 1024,
24, 896, 812, 740. Anal. Calc. for C56H50Cl P Pd : C, 59.02; H,
4 2 2
184, 1094, 812, 741. Anal. Calc. for C52
H42Cl
P
2 2
Pd:ÁC, 68.92; H,
.67. Found: C, 68.83; H, 4.64%.
.42. Found: C, 59.22; H, 4.51%.
2
.2.3. Complex C3
PdCl (CH CN)
nyl)diisopropylphosphine L3 (0.10 mmol, 30 mg). Yield: 87%
2.3.2. Complex C5
PdCl (CH CN)
nyl)diphenylphosphine L2 (0.22 mmol, 86 mg). Yield: 91%
2
3
2
(0.10 mmol, 26 mg) and (E)-(1,2-diphenylvi-
2
3
2
(0.10 mmol, 26 mg) and (E)-(1,2-ditolylvi-
1
1
(
41 mg). Mp: 134–138 °C. H NMR (300 MHz, CDCl3, Me
4
Si)
4
(88 mg). Mp: 190–192 °C. H NMR (300 MHz, CDCl3, Me Si) d
R1
R1
R1
R1
R
R2P
P
C1-C3
1
R
Pd
Cl
C1: R = R =Ph, 89%
CH Cl , rt, 12 h
2
2
Cl
R1
1
C2: R = Tol, R =Ph, 95%
2
1
i
C3: R = Ph, R = Pr, 87%
R1
PdCl (CH CN)
1
2
3
2
R1
R1
C4
:
R = R =Ph, 93%
1
C5: R = Tol, R =Ph, 91%
2
R2P
1
i
R2P
C6: R = Ph, R = Pr, 93%
Cl Pd Cl
PR2
C4-C6
CH Cl , rt, 12 h
2
2
R1
R1
Scheme 1. General scheme of synthesis of (1,2-diaryl) alkenyl phosphine palladium complex C1–C6.