126 Organometallics, Vol. 30, No. 1, 2011
Ayora et al.
CH2), 1.86 (m, 1H, CH2), 1.63-1.49 (om, 2H, 1CH2, 1CH),
1.20-1.00 (om, 3H, CH2), 0.91 (s, 3H, CH3), 0.82 (s, 3H, CH3),
0.80 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) [δ/ppm]
128.24-121.54 (Ar), 81.78 (HCO), 44.91 (CH), 38.36 (NCH3),
35.20 (NCH3), 37.56 (CH2), 28.12 (CH2), 26.68 (CH2), 20.12
(CH3), 18.93 (CH3), 13.68 (CH3).
Selenides. General procedure: 0.15 mmol of ligand dissolved
in 2 mL of toluene in the presence of 1.2 mmol of selenium
powder was stirred for 2 h. Then the reaction mixture was
filtered through Celite. The compounds were characterized by
31P NMR (101 MHz) in toluene solution.
(dd, JHH = 16 JHP = 14, 1H, CH2), 4.79 (dd, JHH = 16, JHP
14, 1H, CH2), 4.70 (m, 1H, HCO) 4.60-4.30 (om, 7H, 6CH2,
1HCO), 4.04 (dd, JHH = 15.6 JHP = 10, 1H, CH2), 3.87 (dd,
JHH = 16.4, JHP = 5.6, 1H, CH2), 3.48 (bs, 1H, CH2), 3.48
(d, JHP = 14, 1H, CH2), 3.35 (bs, 1H, CH2), 3.14 (d, JHP = 14.8,
1H, CH2), 3.18-2.94 (om, 4H, CH), 2.56 (m, 1H, CH2),
2.24-2.18 (om, 3H, CH2), 1.98-1.54 (om, 21H, 2CH, 13CH2,
6CH3), 1.3-0.98 (om, 31H, 13CH2, 18CH3). Anal. Calcd for
C34H48ClN2OPPd (%): C, 60.63; H, 7.18; N, 4.16. Found:
C, 60.92; H, 7.36; N, 4.38. 11b-(R,R,Sal): 2.00 g, yield 75%;
=
1
31P NMR (toluene, 101 MHz) [δ/ppm] 133.5 (s), 131.2 (s); H
Synthesis of Palladium(II) Complexes. [PdCl2L2] (10).PdCl2(cod)
(0.29 g, 1.05 mmol) and 1 g (2.1 mmol) of ligand 7b-(R,R,Sal) were
dissolved in 20 mL of CH2Cl2 at room temperature. After 2 h
stirring, the resulting yellow solution was concentrated under
vacuum and 10 mL of ether was added. The yellow precipitate
was filtered and dried. Yield: 0.98 g (83%); 31P NMR (toluene,
101 MHz) [δ/ppm] 91.84 (s); 1H NMR (CDCl3, 400 MHz) [δ/ppm]
7.63-7.09 (om, 20H, Ar), 4.96 (dt, JHH = 16, JHP = 6.8, 2H, CH2),
4.85 (dt, JHH = 16, JHP = 6.4, 2H, CH2), 4.58-4.81 (m, 2H, OCH),
NMR (CDCl3, 400 MHz) [δ/ppm] 7.62-7.18 (m, 20H, Ar), 4.98
(m, 1H, HCO), 4.82 (m, 2H, CH2), 4.6-4.3 (om, 7H, 6CH2,
1HCO), 4.05 (dd, JHH = 16, JHP = 8.4, 1H, CH2), 3.70 (dd,
JHH = 16.4, JHP = 5.4, 1H, CH2), 3.44 (d, JHP = 14, 1H, CH2),
3.41 (bs, 1H, CH2), 3.37 (bs, 1H, CH2), 3.19 (d, JHP = 14, 1H,
CH2), 3.10 (m, 2H, CH), 2.99 (m, 2H, CH), 2.39 (bs, 1H, CH2),
2.28 (bs, 1H, CH2), 2.25-1.41 (om, 22H, 14CH2, 2CH, 6CH3),
1.38-0.90 (om, 13H, CH2), 0.91-0.82 (om, 19H, 1CH2,
18CH3). Anal. Calcd for C34H48ClN2OPPd (%): C, 60.63; H,
7.18; N, 4.16. Found: C, 59.58; H, 7.23; N, 3.89.
4.40 (dt, JHH = 16, JHP = 6, 2H, CH2), 4.08 (dt, JHH = 16.4, JHP
=
2.4, 2H, CH2), 3.20 (m, 2H, CH), 2.98 (m, 2H, CH), 2.27 (m, 1H,
CH2), 2.08 (m, 1H, CH2), 1.76-0.86 (om, 28H, 26CH2, 2CH), 0.85
(s, 6H, CH3), 0.80 (s, 6H, CH3), 0.79 (s, 6H, CH3). Anal. Calcd for
C60H82Cl2N4O2P2Pd (%): C, 63.74; H, 7.31; N, 4.96. Found: C,
63.53; H, 7.59; N, 4.95.
11c-(R,R,Sal) was synthesized in a similar way to that used
for 11b. Starting materials: 0.48 g (1.2 mmol) of [Pd(η3-2-
CH3C3H4)(μ-Cl)]2and 1.02 g (2.38 mmol) of ligand 7c-(R,R,Sal).
Yield: 1.07 g (72%); 31P NMR (toluene, 101 MHz) [δ/ppm]
134.3 (s), 133.9 (s); 1H NMR (CDCl3, 400 MHz) [δ/ppm]
7.55-7.15 (m, 20H, Ar), 5.09 (dq, JHP = 12.4 JHH = 6.4, 1H,
[PdCl(η3-2-CH3C3H4)L] (11-14). The complexes were ob-
tained by similar procedures described in the literature.30
For 11a-(R,R,Ral), 11a-(S,S,Sal), 11a-(R,R,Sal), and 11a-(S,S,
Ral), 0.22 g (0.6 mmol) of [Pd(η3-2-CH3C3H4)(μ-Cl)]2 was
dissolved in 5 mL of toluene and 0.5 g (1.1 mmol) of ligand 7a
dissolved in 5 mL of CH2Cl2 was added. The mixture was stirred
at 0 °C for 2 h, and the solvent removed under reduced pressure.
Addition of ether (10 mL) led to a brown solid. 11a-(R,R,Ral):
yield 0.48 g (67%). 11a-(S,S,Sal): yield 0.43 g (60%); 31P NMR
(toluene, 101 MHz) [δ/ppm] 126.7 (s), 126.2 (s); 1H NMR
(CDCl3, 400 MHz) [δ/ppm] 7.50-7.03 (m, 30H, Ar), 5.27
(m, 1H, OCH), 5.21 (m, 1H, OCH), 4.95 (dd, JHH = 15.2,
CH), 4.94 (dq, JHP = 12.4, JHH = 6.4, 1H, CH), 4.74 (pt, JHP
=
JHH = 16.4, 2H, CH2), 4.61-4.31 (om, 6H, CH2), 4.19
(dd, JHP = 16, JHH = 9.6, 1H, CH2), 4.04 (dd, JHP = 16.4,
J
HH = 6, 1H, CH2), 3.63 (s, 3H, CH3), 3.59 (s, 3H, CH3), 3.52
(bs, 2H, CH2), 3.44 (d, JHP = 14, 1H, CH2), 3.25 (d, JHP = 14.4,
1H, CH2), 3.11-3.03 (m, 4H, CH), 2.52 (bs, 1H, CH2), 2.31
(bs, CH2), 1.83-1.50 (om, 14H, 6CH3, 8CH2), 1.38 (d, JHH
=
6.8, 6H, CH3), 1.25-1.04 (om, 8H, CH2). Anal. Calcd for
C28H38ClN2O3PPd (%): C, 55.36; H, 6.31; N, 4.61. Found: C,
53.11; H, 6.44; N, 4.57.
11d-(R,R) was synthesized in a similar way to that used
for 11b. Starting materials: 0.42 g (1.05 mmol) of [Pd(η3-2-
CH3C3H4)(μ-Cl)]2 and 0.82 g (2.16 mmol) of ligand 7d-(R,R).
Yield: 0.27 g (44%); 31P NMR (toluene, 101 MHz) [δ/ppm]
129.0 (s), 128.6 (s); 1H NMR (CDCl3, 400 MHz) [δ/ppm]
7.48-7.13 (om, 20H, Ar), 5.13-5.05 (om, 4H, CH2), 4.81-
4.66 (om, 2H, CH2), 4.44-4.38 (om, 8H, CH2), 3.32 (m, 1H,
CH2), 3.17-3.14 (om, 3H, 2CH, 1CH2), 3.01-2.98 (om, 4H,
2CH, 2CH2), 2.18 (bs, 2H, CH2), 2.04 (bs, 2H, CH2), 1.76 (s, 3H,
CH3), 1.60 (s, 3H, CH3), 1.86-1.08 (om, 16H, CH2); MS/ESI (þ)
(m/z) 541.1601 [(M - Cl)]þ. Anal. Calcd for C27H36ClN2OPPd
(%): C, 56.16; H, 6.28; N, 4.86. Found: C, 56.35; H, 6.69;
N, 5.10.
JHP = 12, 1H, CH2), 4.83 (dd, JHH=15.2, JHP=12.4, 1H, CH2),
4.34-4.21 (om, 3H, CH2), 4.13 (pt, JHH=JHP=16, 1H, CH2),
3.80 (m, 1H, CH2), 3.54 (dd, JHH=16 JHP = 12, 1H, CH2), 3.42
(d, JHP = 14.4, 1H, CH2), 3.37 (bs, 1H, CH2), 3.25 (bs, 1H,
CH2), 3.09 (m, 2H, CH), 2.94 (d, JHP = 14.4, 1H, CH2), 2.92
(m, 1H, CH2), 2.77 (m, 2H, CH), 2.52 (dd, JHH = 16.4
JHP = 6.4, 1H, CH2), 2.43 (bs, 1H, CH2), 2.08 (bs, 1H, CH2),
1.86 (s, 3H, CH3), 1.47 (s, 3H, CH3), 1.14 (d, JHH = 6.4, 3H,
CH3), 1.01 (d, JHH = 6.4, 3H, CH3), 1.63-0.71 (om, 16H, CH2).
Anal. Calcd for C32H40ClN2OPPd (%): C, 59.91; H, 6.28; N,
4.37. Found: C, 59.63; H, 6.71; N, 4.02. 11a-(R,R,Sal): yield 0.24
g (34%). 11a-(S,S,Ral): yield 0.17 g (24%); 31P NMR (toluene,
1
101 MHz) [δ/ppm] 130.7 (s), 130.0 (s); H NMR (CDCl3, 400
11f-(R,R) was synthesized in a similar way to that used for 11b
and precipitated in ether. Starting materials: 0.41 g (1.05 mmol)
of [Pd(η3-2-CH3C3H4)(μ-Cl)]2 and 0.84 g (2.09 mmol) of ligand
7f-(R,R). Yield: 0.31 g (51%); 31P NMR (toluene, 101 MHz)
[δ/ppm] 120.0 (s), 118.2 (s); 1H NMR (CDCl3, 400 MHz)
[δ/ppm] 7.66-7.13 (om, 30H, Ar), 4.80 (pq, JHP = JHH = 15.6,
2H, CH2), 4.52-5.37 (om, 4H, CH2), 4.29 (pt, JHP = JHH = 14,
MHz) [δ/ppm] 7.44-6.96 (m, 30H, Ar), 5.64 (m, 1H, CH), 5.52
(m, 1H, CH), 4.65-4.55 (om, 2H, CH2), 4.42-4.20 (om, 6H,
CH2), 3.79 (dd, JHH = 16.0 JHP = 8, 1H, CH2), 3.70 (dd, JHH =
16.8 JHP = 5.6, 1H, CH2), 3.32 (d, JHP = 14.0, 1H, CH2), 3.32
(bs, 1H, CH2), 3.24 (bs, 1H, CH2), 3.17 (d, JHP = 14.0, 1H,
CH2), 3.08-2.94 (om, 4H, CH), 2.21 (bs, 2H, CH2), 1.72 (s, 3H,
CH3), 1.66 (s, 3H, CH3), 1.63-1.45 (om, 8H, CH2), 1.45
(d, JHH=6.4, 6H, CH3), 1.18-0.94 (om, 8H, CH2). Anal. Calcd
for C32H40ClN2OPPd (%): C, 59.91; H, 6.28; N, 4.37. Found: C,
59.63; H, 6.71; N, 4.02.
1H, CH2), 4.19 (pt, JHP = JHH = 14, 1H, CH2), 3.71 (dd, JHH
15.2 JHH = 9.6, 1H, CH2), 3.47 (m, 1H, CH2), 3.35 (d, JHP
=
=
11.6, 1H, CH2), 3.31 (d, JHP = 12, 1H, CH2), 3.19 (m, 1H, CH),
3.06 (m, 1H, CH), 2.94 (bs, 1H, CH2), 2.86 (bs, 1H, CH2), 2.81
(m, 1H, CH), 2.72 (m, 1H, CH), 2.10 (bs, 1H, CH2), 2.00 (bs, 1H,
CH2), 1.78 (bs, 6H, CH3), 1.73-1.08 (om, 16H, CH2); MS/ESI (þ)
(m/z) 561.1726 [(M - Cl)]þ. Anal. Calcd for C30H36ClN2PPd
(%): C, 60.31; H, 6.07; N, 4.69. Found: C, 57.26; H, 5.77; N,
4.12.
12b-(R,R,Sal) was synthesized in a similar way to that used
for 11b Starting materials: 0.75 g (1.9 mmol) of [Pd(η3-2-
CH3C3H4)(μ-Cl)]2 and 1.24 g (3.8 mmol) of ligand 8b-(R,R,Sal).
Yield: 1.39 g (70%); 31P NMR (toluene, 101 MHz) [δ/ppm]
For 11b-(R,R,Ral) and 11b-(R,R,Sal), 1.90 g (4.0 mmol) of
ligand 7b dissolved in toluene (5 mL) was added to a solution of
0.78 g (2.0 mmol) of [Pd(η3-2-CH3C3H4)(μ-Cl)]2 in 5 mL of
CH2Cl2. The mixture was stirred at 0 °C for 2 h, and the solution
was dried under reduced pressure. The resulting orange residue
was washed with pentane (3 ꢀ 20 mL), giving the desired pro-
duct as an orange solid. 11b-(R,R,Ral): yield 1.86 g (70%);
1
31P NMR (toluene, 101 MHz) [δ/ppm] 130.0 (s), 129.9 (s); H
NMR (CDCl3, 400 MHz) [δ/ppm] 7.73-7.13 (m, 20H, Ar), 4.87