Ligands 4 and 5 were prepared according to the same procedure
followed for 3.
were obtained after the diffusion of petroleum ether into a
chloroform solution of Pd(3)Cl2. Yield 0.36 g (83%). Found: C,
50.36; H, 4.59. C23H25Cl2PPdS requires C, 50.99; H, 4.65%. dP
Data for 4. 3,5-Dimethylbenzylbromide (1.0 g, 5.0 mmol) was
used. Yield 1.41 g (72%). dP (CH2Cl2–D2O insert, 121 MHz) −20.8;
dH (CDCl3, 400 MHz) 0.84 (3H, t, 3JHH = 7.3, CH2CH3), 1.59 (1H,
m, CH2CH3), 1.71 (1H, m, CH2CH3), 2.16 (6H, s, CH3), 2.24 (1H,
(CDCl3, 300 MHz) 50.7; dH (CDCl3, 400 MHz) 0.94 (3H, t, 3JHH
=
7.3, CH2CH3), 1.73 (1H, m, CH2CH3), 1.82 (1H, m, CH2CH3),
2
2.34 (1H, m), 2.56 (2H, m), 3.95 (1H, d, JHH = 13.6, CH2Ph),
2
4.90 (1H, d, JHH = 13.6, CH2Ph), 7.05–7.70 (15H, m, Ar); dC
2
3
2
m, JHH = 13.6, JHH = 8.5, PCH2), 2.33 (1H, m, JHH = 13.6,
(CDCl3, 100 MHz) 9.9 (1C, s, CH3), 24.7 (1C, s, CH2), 27.0 (1C,
3JHH = 6.2, PCH2), 2.47 (1H, m, CHEt), 3.47 (1H, d, 2JHH = 13.0,
1
2
d, JCP = 8.0 Hz, CH2), 34.1 (1C, d, JCP = 15.0, CH), 43.1 (1C,
2
CH2Xyl), 3.52 (1H, d, JHH = 13.0, CH2Xyl), 6.73 (1H, s, Xyl),
4
d, JCP = 15.0, CH2), 127.1 (1C, s), 128.3–128.9 (6C, m), 132.0
7.2–7.7 (12H, m, Ar); dC (CDCl3, 75 MHz) 12.3 (1C, s, CH3), 21.4
(2C, s, CH3), 26.2 (1C, d, 1JCP = 16.2 Hz, CH2), 29.8 (1C, s, CH2),
(2C, m), 132.2 (2C, m), 138.0 (2C, m), 138.3 (1C, m); m/z (ES)
505.0132 (M − Cl+. C23H25ClPPdS requires 505.0129), 439 (14%).
2
37.5 (1C, d, JCP = 34.0, CH), 41.4 (1C, br, CH2), 128.1 (2C, s),
128.9 (2C, d, JCP = 16.9), 129.1 (2C, d, JCP = 15.4), 130.6 (2C, s),
132.2 (2C, m), 133.2 (2C, d, JCP = 13.8), 138.7 (2C, s); m/z (ES)
393.1793 (MH+. C25H30PS requires 393.1806), 287 (65%).
Pd(4)Cl2. Pd(PhCN)2Cl2 (1.15 g, 3.0 mmol) was added to a
dichloromethane solution (10 mL) of 4 (1.18 g, 3.0 mmol) and
the reaction was left to stir overnight. Subsequently, the solvents
were removed in vacuo and the yellow solid formed was washed
with diethyl ether (20 mL) and dried. The pure compound was
obtained after slow diffusion of petroleum ether into a chloroform
solution of Pd(4)Cl2. Yield 1.50 g (87%). Found: C, 52.33; H, 5.10.
C25H29Cl2PPdS requires C, 52.69; H, 5.13%. dH (CDCl3, 500 MHz)
Data for 5. 1-Chloromethylnapthalene (0.38 mL, 2.5 mmol)
was used. Yield 0.65 g (63%). dP (CH2Cl2–D2O insert, 121 MHz)
−20.5; dH (CDCl3, 400 MHz) 0.81 (3H, t, 3JHH = 7.3, CH2CH3),
1.62 (1H, m, CH2CH3), 1.75 (1H, m, CH2CH3), 2.28 (1H, m,
2JHH = 13.8, 3JHH = 8.5, PCH2), 2.38 (1H, m, 2JHH = 13.8, 3JHH
=
3
6.3, PCH2), 2.51 (1H, m, CHEt), 3.95 (1H, d, 2JHH = 13.0, CH2Ph),
4.05 (1H, d, 2JHH = 13.0, CH2Ph), 7.05 (1H, d, 3JHH = 8.1), 7.17
0.95 (3H, t, JHH = 7.3, CH2CH3), 1.65 (1H, m, CH2CH3), 1.79
(1H, m, CH2CH3), 2.14 (6H, s, CH3), 2.28 (1H, m), 2.66 (2H,
m), 3.88 (1H, d, 2JHH = 13.5, CH2Xyl), 4.70 (1H, d, 2JHH = 13.5,
CH2Xyl), 6.69 (1H, s, Xyl), 7.17 (2H, s, Xyl), 7.3–7.6 (10H, m,
ArH); dC (CDCl3, 100 MHz) 12.3 (1C, s, CH3), 21.3 (2C, s, CH3),
3
3
(1H, d, JHH = 8.3), 7.2–7.5 (12H, m, Ar), 7.62 (1H, d, JHH
=
8.3), 7.74 (1H, m), 8.04 (1H, d, 3JHH = 8.4); dC (CDCl3, 100 MHz)
9.7 (1C, s, CH3), 27.0 (1C, d, 1JCP = 9.1, CH2), 33.5 (1C, s, CH2),
34.3 (1C, d, 2JCP = 10.1, CH), 43.8 (1C, d, 4J = 15.1, CH2), 123.2
(1C, s), 124.1 (1C, s), 124.7 (1C, s), 125.0 (1C, s), 126.8 (1C, s),
127.2–127.7 (6C, m), 130.2 (1C, d, JCP = 9.2), 130.4 (1C, s), 130.8
(1C, m), 131.7 (2C, d, JCP = 13.3), 131.9 (2C, d, JCP = 10.6), 132.9
1
2
26.1 (1C, d, JCP = 16.1, CH2), 31.0 (1C, s), 37.3 (1C, d, JCP
=
34.2, CH), 41.3 (1C, s, CH2), 128.0 (2C, s), 128.9 (2C, d, JCP
=
12.0), 129.1 (2C, d, JCP = 11.3), 130.6 (2C, s), 132.1(2C, m), 133.1
(2C, d, JCP = 10.1), 138.6 (2C, s); dP (CDCl3, 121 MHz) 52.4; m/z
(ES) 533.0445 (M − 35Cl+. C25H29ClPPdS requires 533.0445), 588
(1C, d, JCP = 11.7), 137.4 (1C, d, JCP = 13.8), 137.5 (1C, d, JCP
13.9); m/z (ES) 415.1647 (MH+. C27H28PS requires 415.1649).
=
+
(M + NH4 , 20%).
[Pd(1)I]2. To a 20 mL ethanol solution of [Pd(1)Cl]2 (0.42 g,
0.5 mmol) a methanol solution (1M) of potassium iodide (0.83 g,
5.0 mmol) was added and stirred overnight. As the reaction
progressed the colour of the solution changed from yellow to
orange and a precipitate was formed. Evaporation of the solvents
left an orange solid, which was subsequently extracted with
dichloromethane (2 × 10 mL) and filtered. The filtrate was
evaporated to dryness to afford the iodide dimer as a red solid.
Crystals of the complex were obtained after slow diffusion of ether
to a dichloromethane solution of [Pd(1)I]2. Yield 0.42 g (83%).
Found: C, 37.54; H, 3.56. C32H36I2P2Pd2S2 requires C, 37.93; H,
3.58%. dP (CDCl3, 300 MHz) 43.5; dH (CDCl3, 400MHz) 0.97
Pd(5)Cl2. To a solution of Pd(PhCN)2Cl2 (0.32 g, 0.83 mmol)
in 20 mL of dichloromethane 5 (0.83 mmol) was added. The orange
solution was allowed to stir overnight. Subsequently the volume of
the solution was reduced to ca. 10 mL and diethyl ether (20 mL)
was added to precipitate the product as an orange solid. Yield
0.34 g (69%). Found: C, 53.93; H, 4.55. C27H27Cl2PPdS requires C,
54.79; H, 4.60%. dP (D2O insert, 121 MHz) 54.2; dH (CDCl3, 400
MHz) 0.58 (3H, t, 3JHH = 7.3, CH2CH3), 1.24 (2H, m, CH2CH3),
2.32 (1H, m, PCH2), 2.55 (2H, m, PCH2/CHEt), 4.77 (1H, d,
2JHH = 13.8, CH2Ph), 5.14 (1H, d, 2JHH = 13.8, CH2Ph), 7.2–7.7
(14H, m, Ar), 7.71 (1H, d, 3JHH = 8.0), 7.76 (1H, d, 3JHH = 8.0),
8.43 (1H, d, 3JHH = 8.3); dC (CDCl3, 75 MHz) 12.3 (1C, s, CH3),
27.3 (1C, m, CH2), 38.8 (1C, m, CH), 41.9 (1C, s, CH), 49.5 (1C,
m, CH2), 124.3 (1C, s), 125.0 (1C, s), 126.8 (1C, s), 127.7 (1C,
s), 128.9–129.1 (6C, m), 130.2 (1C, br), 131.1 (1C, br), 132.4 (2C,
m), 133.1 (4C, m), 133.9 (1C, m); m/z (ES) 555.0279 (M − Cl+.
C27H27ClPPdS requires 555.0294).
3
2
3JHH = 7.5,
∼
(3H, t, JHH = 7.4, CH2CH3), 1.69 (1H, m, JHH
=
CH2CH3), 1.94 (1H, m, CH2CH3), 2.70 (1H, ddd, 2JHH 3JHH
=
∼
=
2
2
6.54, JHP = 13.48, PCH2), 2.99 (1H, ddd, JHH 2JHP = 11.59,
∼
=
3JHH = 3.93, PCH2), 3.89 (1H, br m, CHEt), 7.30 (2H, m, ArH),
7.42 (4H, m, ArH), 7.83 (4H, m, ArH); dC (CDCl3, 100 MHz)
11.48 (1C, s, C1), 28.58 (1C, m, C2), 46.15 (1C, m), 46.39 (1C, s),
127.84 (1C, m), 127.97 (1C, m), 130.51 (1C, s), 132.63 (1C, m);
m/z (ES) 1012.8002 (MH+. C32H37I2P2Pd2S2 requires 1012.7981),
1015 (8%), 887 (M+ − I, 15).
General procedure for the Suzuki reaction
A 1,4-dioxane (5 mL) solution containing 4-bromotoluene
(5 mmol), benzene boronic acid (7 mmol), base (7 mmol),
naphthalene (2.5 mmol, used as GC standard) and catalyst
Pd(3)Cl2. Pd(PhCN)2Cl2 (0.31 g, 0.8 mmol) was added to a
dichloromethane solution (10 mL) of 3 (0.29 g, 0.8 mmol). The
resulting orange solution was left stirring overnight. Subsequently,
the solvents were evaporated to afford an oil, which was triturated
with diethyl ether (2 × 10 mL) and dried. Crystals of the complex
R
was introduced into an ACEꢀ glass pressure tube which was
subsequently sealed, stirred and heated at the stated temperature.
The course of the reaction was monitored by GC-MS; samples
5722 | Dalton Trans., 2006, 5717–5724
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The Royal Society of Chemistry 2006
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