Macromolecules, Vol. 38, No. 15, 2005
Palladium and Platinum Coordination Polymers 6297
Ph), 128.33 (d, 2C, Ph), 31.94 (s, 1C, alkyl), 31.24 (d, 1C, alkyl),
29.68 (s, 1C, alkyl), 29.64 (s, 1C, alkyl), 29.37 (m, 3C, alkyl)
29.28 (s, 1C, alkyl), 28.06 (d, 1C, alkyl), 26.05 (d, 1C, alkyl),
22.72 (s, 1C, alkyl), 14.15 (s, 1C, alkyl). δP (162 MHz): -16.0
(s, 1P).
H2CH2O), 1.38-1.28 (m, 18H, CH2), 0.91 (t, 3H, CH3). δC (75
MHz): 142.32 (d, 2C, Ph), 130.43 (d, 4C, Ph), 129.29 (s, 2C,
Ph), 128.40 (d, 4C, Ph), 70.43 (d, 1C, CH2O), 32.08 (s, 1C,
alkyl), 31.59 (d, 1C, alkyl), 29.80-29.46 (m, 6C, alkyl), 25.99
(s, 1C, alkyl), 22.84 (s, 1C, alkyl), 14.28 (s, 1C, alkyl). δP (162
MHz): 112.4 (s, 1P).
1,12-Bis(diphenylphosphino)dodecane (2). 1,12-Dibro-
mododecane (3.28 g, 10.0 mmol) was dissolved in dry THF (50
mL), and the stirred solution was cooled to -78 °C with
acetone/dry ice. A solution of potassium diphenylphosphide in
THF (0.5 M, 40.0 mL, 20.0 mmol) was slowly added to the
mixture. After complete addition, the mixture was stirred for
an hour at -78 °C and left to warm to room temperature. The
mixture was stirred overnight. Solvent was removed in vacuo,
and the solids were suspended in dry dichloromethane (40 mL)
and filtered over a glass filter. Solvent was removed in vacuo.
White crystals were obtained in 88% yield by recrystallization
from boiling acetonitrile. δH (400 MHz): 7.47-7.28 (m, 20H,
Ph), 2.01 (t, 4H, CH2P), 1.47-1.18 (m, 20H, CH2). δC (121
MHz): 139.44 (d, 4C, Ph) 133.05 (d, 8C, Ph), 128.76 (s, 8C,
Ph), 128.70 (d, 4C, Ph), 31.57 (d, 2C, CH2P), 29.88 (d, 2C,
alkyl), 29.60 (s, 4C, alkyl), 28.40 (d, 2C, alkyl), 26.32 (d, 2C,
alkyl). δP (162 MHz): -16.0 (s, 2P). Elemental analysis calcd
(%) for C36H44P2: C 80.27, H 8.23. Found: C 79.83, H 7.97.
1-(Dicyclohexylphosphino)dodecane (3). Dicyclohexyl-
phosphine (2.00 g, 10.1 mmol) was dissolved in 50 mL of dry
THF and cooled to -78 °C, and n-butyllithium (1.6 M, 6.3 mL,
10 mmol) was added. This mixture was left to warm to room
temperature and then added to an ice-cooled 0 °C mixture of
1-bromododecane (2.51 g, 10.1 mmol) in 50 mL of dry THF.
This mixture was stirred for 30 min and left to warm to room
temperature. Solvent was removed in vacuo, and the solids
were suspended in dry diethyl ether (50 mL). To remove
residual impurities, the mixture was filtered over silica that
was dried from water and air. Solvent was removed in vacuo.
The product, a clear liquid, was obtained in 63% yield. δH (400
MHz, toluene-d8): 2.07-1.43 (m, 44H, CH2 + CH), 1.15 (t, 3H,
CH3). δC (75 MHz, toluene-d8): 34.50 (d, 2C, alkyl), 32.86 (s,
1C, alkyl), 32.55 (d, 1C, alkyl), 31.31 (d, 2C, alkyl), 30.67 (d,
4C, alkyl), 30.42 (d, 2C, alkyl), 29.92 (d, 2C, alkyl), 29.67 (d,
1C, alkyl), 28.30-28.14 (m, 4C, alkyl), 27.47 (s, 2C, alkyl),
23.62 (s, 1C, alkyl), 22.55 (d, 1C, alkyl), 14.80 (s, 1C, CH3). δP
(162 MHz, toluene-d8): -4.8 (s, 1P).
1,12-Bis(dicyclohexylphosphino)dodecane (4). Dicyclo-
hexylphosphine (3.0 g, 15 mmol, 2 equiv) was dissolved in 50
mL of dry THF. This solution was cooled to -78 °C, and
n-butyllithium (1.6 M, 9.5 mL, 15 mmol) was added. This
mixture was left to warm to room temperature and then added
to an ice-cooled mixture of 1,12-dibromododecane (2.5 g, 7.6
mmol) in 50 mL of dry THF. This mixture was stirred for 30
min and left to warm to room temperature. Solvent was
removed in vacuo, and the solids were suspended in dry diethyl
ether (50 mL). To remove residual impurities, the mixture was
filtered over silica that was dried from water and air. Solvent
was removed in vacuo. The product, a clear liquid, was
obtained in 50% yield. The liquid crystallized when cooled to
4 °C. δH (200 MHz): 2.25-1.31 (m, 68H, CH2 + CH). δC (100
MHz): 33.44 (d, 4C, PCH), 31.73 (d, 2C, alkyl), 30.49 (d, 4C,
alkyl), 29.73 (d, 4C, alkyl), 29.49 (s, 2C, alkyl), 29.12 (d, 4C,
alkyl), 28.63 (d, 2C, alkyl), 27.58-27.42 (m, 8C, alkyl), 26.70
(s, 4C, alkyl), 21.40 (d, 2C, PCH2). δP (162 MHz, toluene-d8):
-4.8 (s, 2P).
1,12-Bis(diphenylphosphinito)dodecane (6). 1,12-Dode-
canediol (2.50 g, 12.4 mmol) was dried from water by coevapo-
ration with dry toluene and subsequently dissolved in 100 mL
of dry THF. Triethylamine (2.49 g, 24.7 mmol, 2 equiv) was
added, and the stirred solution was cooled to 0 °C with ice.
Chlorodiphenylphosphine (5.45 g, 24.7 mmol, 2 equiv) was
slowly added to the mixture. After complete addition, the
solution was stirred for an hour at 0 °C and left to warm to
room temperature. Solvent was removed in vacuo, and the
solids were suspended in dry dichloromethane (50 mL). To
remove the triethylamine salt, the mixture was filtered over
silica that was dried from water and air. Solvent was removed
in vacuo. The product, a clear liquid, was obtained in 48%
yield. The liquid crystallized when cooled to 5 °C. δH (400
MHz): 7.57-7.35 (m, 20H, Ph), 3.93-3.87 (m, 4H, CH2O),
1.77-1.70 (m, 4H, CH2CH2O), 1.41-1.29 (m, 16H, CH2). δC
(75 MHz): 142.41 (d, 2C, Ph), 130.40 (d, 4C, Ph), 129.26 (s,
2C, Ph), 128.37 (d, 4C, Ph), 70.38 (d, 2C, CH2O), 31.55 (d, 2C,
alkyl), 29.65-29.41 (m, 6C, alkyl), 25.96 (s, 2C, alkyl) δP (162
MHz): 112.4 (s, 2P).
Palladium Dichloride Bis(1-(diphenylphosphino)dode-
cane) (7). A mixture of palladium(II) dichloride (37 mg, 0.21
mmol, 0.55 equiv) and 1-(diphenylphosphino)dodecane (133
mg, 0.375 mmol) in dry dichloromethane (7 mL) was stirred
for 24 h. The mixture was filtered in order to remove the excess
palladium(II) dichloride, and solvent was removed in vacuo,
yielding a bright yellow solid in 92% yield. δH (400 MHz):
7.70-7.22 (m, 20H, Ph), 2.41-2.27 (m, 4H CH2P), 1.28-0.98
(m, 40H, CH2), 0.91 (t, 6H, CH3). δC (121 MHz): 133.83 (s,
2C, Ph), 130.61 (d, 4C, Ph), 128.34 (s, 4C, Ph), 128.28 (s, 2C,
Ph), 32.08 (s, 1C, alkyl), 31.38 (d, 1C, alkyl), 29.79-29.42 (m,
6C, alkyl), 28.21 (d, 1C, alkyl), 26.12 (d, 1C, alkyl), 22.85 (s,
1C, alkyl), 14.28 (s, 1C, alkyl). δP (162 MHz): 16.5 (s, 2P).
Elemental analysis calcd (%) for C48H70Cl2P2Pd: C 65.04, H
7.96. Found: C 64.84, H 7.91. MALDI-TOF MS: 851.5
(M+ - Cl).
Palladium Dichloride Bis(1-(dicyclohexylphosphino)-
dodecane) (8). A mixture of palladium(II) dichloride (56 mg,
0.32 mmol, 0.55 equiv) and 1-(dicyclohexylphosphino)dodecane
(210 mg, 0.571 mmol) in dry dichloromethane (10 mL) was
stirred for 48 h. The mixture was filtered in order to remove
the excess palladium(II) dichloride, and solvent was removed
in vacuo, yielding an orange oil in 99% yield. δH (400 MHz):
2.30-1.25 (m, 88H, CH2 + CH), 0.94 (t, 6H, CH3). δC (75
MHz): 33.25-32.94 (m, 4C, alkyl), 32.08 (s, 4C, alkyl), 29.83-
29.44 (m, 18C, alkyl), 29.07 (s, 4C, alkyl), 27.57-27.41 (m, 8C,
alkyl), 26.62 (s, 4C, alkyl), 25.52 (s, 2C, alkyl), 22.85 (s, 2C,
alkyl), 14.27 (s, 2C, CH3). δP (162 MHz): 21.8 (s, 2P). Elemental
analysis calcd (%) for C48H94Cl2P2Pd: C 63.32, H 10.41.
Found: C 63.10, H 10.67.
Palladium Dichloride Bis(1-(diphenylphosphinito)-
dodecane) (9). A mixture of palladium(II) dichloride (74 mg,
0.41 mmol, 0.53 equiv) and 1-(diphenylphosphinito)dodecane
(0.28 g, 0.79 mmol) in dry dichloromethane (20 mL) was stirred
for 48 h. The mixture was filtered in order to remove the excess
palladium(II) dichloride, and solvent was removed in vacuo,
yielding a bright yellow solid in 99% yield. δP (300 MHz):
7.87-7.42 (m, 40H, Ph), 3.68 (q, 2H, CH2O), 1.37-1.13 (m,
40H, CH2), 0.92 (t, 3H, CH3). δC (75 MHz): 133.16-128.12 (m,
20C, Ph), 69.40 (s, 1C, CH2O), 31.86 (s, 1C, alkyl), 30.01-29.07
(m, 8C, alkyl), 25.37 (s, 1C, alkyl), 22.63 (s, 1C, alkyl), 14.08
(s, 1C, alkyl). δP (162 MHz): 110.0 (s, 2P).
1-(Diphenylphosphinito)dodecane (5). 1-Dodecanol (2.5
g, 13 mmol), which was dried from water with dry toluene,
and 1.9 mL of triethylamine (1.4 g, 13 mmol) were dissolved
in dry THF (50 mL), and the stirred solution was cooled to 0
°C with ice. Chlorodiphenylphosphine (3.0 g, 13.4 mmol) was
slowly added to the mixture. After complete addition, the
solution was stirred for an hour at 0 °C and left to warm to
room temperature. Solvent was removed in vacuo, and the
solids were suspended in dry dichloromethane (50 mL). To
remove residual impurities, the mixture was filtered over silica
that was dried from water and air. Solvent was removed in
vacuo. The product was obtained as a clear liquid in 90% yield.
The liquid crystallizes when cooled to 5 °C. δH (400 MHz):
7.54-7.34 (m, 10H, Ph), 3.87 (q, 2H, CH2O), 1.71 (t, 2H, C
Platinum Dichloride Bis(1-(diphenylphosphino)dode-
cane) (10). A mixture of platinum(II) dichloride (30.5 mg,
0.114 mmol, 0.50 equiv) and 1-(diphenylphosphino)dodecane
(81.0 mg, 0.228 mmol) in dry dichloromethane (5 mL) was
stirred for 24 h. The mixture was filtered in order to remove
the residual platinum(II) dichloride, and solvent was removed
in vacuo, yielding a light brown solid in 84% yield. δH (400