Pd Complexes of 1,3-Bis(diphenylphosphino)propane
Organometallics, Vol. 21, No. 20, 2002 4157
viscous oil in 80% yield (1.72 g), according to the procedure
described above for 1a . 31P{1H} NMR (121.4 MHz, CDCl3, δ):
-24.3 (s). 1H NMR (300.0 MHz, CDCl3, δ): 7.35 (m, 8H, C6H5),
7.10 (m, 12H, C6H5), 3.02 (s, 2H, CH2), 2.75 (s, 3H, CH3), 2.32
(dd, 2H, J ) 14.3, 2.5 Hz, CH2), 2.27 (dd, 2H, J ) 14.3 Hz, 2.5
Hz, CH2), 0.90 (s, 3H, CH3).
Syn t h esis of [{2-Met h oxym et h yl-2-m et h yl-1,3-b is(d i-
p h en ylp h osp h in o)p r op a n e}P d (OAc)2] (3b). Compound 3b
was prepared according to the procedure described above for
3a and was isolated as a tan solid in 87% yield (1.31 g). 31P{1H}
1
NMR (121.4 MHz, CDCl3, δ): 16.3 (s, PPh2). H NMR (300.0
MHz, CDCl3, δ): 7.82 (m, 8H, C6H5), 7.36 (m, 12H, C6H5), 2.97
(s, 3H, OCH3), 2.78 (s, 2H, OCH2), 2.46 (m, 2H, CH2), 2.10 (m,
2H, CH2), 1.48 (br s, 6H, O2CCH3), 0.82 (s, 3H, CH3).
Syn th esis of 2-Meth yl-2-p h en yl-1,3-bis(d ip h en ylp h os-
ph in o)pr opan e (1c). 2-Methyl-2-phenyl-1,3-bis(diphenylphos-
phino)propane was isolated as a colorless, viscous oil in 79%
yield (1.39 g), according to the procedure described above for
Syn t h esis of [{2-Met h yl-2-p h en yl-1,3-b is(d ip h en yl-
p h osp h in o)p r op a n e}P d (OAc)2] (3c). Compound 3c was
prepared according to the procedure described above and was
isolated as a white solid in 83% yield (0.9 g). 31P{1H} NMR
1
1a . 31P{1H} NMR (121.4 MHz, CDCl3, δ): -23.0 (s). H NMR
(300.0 MHz, CDCl3, δ): 7.34-6.94 (m, 25H, C6H5), 2.71 (dd,
2H, J ) 14.4 Hz, 4.0 Hz, CH2), 2.62 (dd, 2H, J ) 14.4 Hz, 4.0
Hz, CH2), 1.42 (s, 3H, CH3).
1
(121.4 MHz, CDCl3, δ): 16.8 (s, PPh2). H NMR (300.0 MHz,
CDCl3, δ): 8.06 (m, 4H, C6H5), 7.63 (m, 4H, C6H5), 7.45-7.05
(m, 17H, C6H5), 2.67 (dd, 2H, J ) 7.6 Hz, 14.9 Hz, CH2), 2.55
(dd, 2H, J ) 7.6 Hz, 14.9 Hz, CH2), 1.45 (br s, 6H, O2CCH3),
1.10 (s, 3H, CH3).
Syn th esis of [{1,3-Bis(d ip h en ylp h osp h in o)p r op a n e}-
P d (OAc)2}] (3d ). Compound 3d was prepared according to
the procedure described above and isolated as a white solid in
77% yield (2.24 g). 31P{1H} NMR (121.4 MHz, CDCl3, δ): 10.5
(s, PPh2). 1H NMR (300.0 MHz, CDCl3, δ): 7.33-7.18 (m, 20H,
C6H5), 2.12 (m, 4H, CH2), 1.59 (m, 2H, CH2).
Syn th esis of [{2-Meth yl-2-pyr idin -2-yl-1,3-bis(diph en yl-
p h osp h in o)p r op a n e}P d Cl2] (2a ). A solution of [(cycloocta-
1,5-diene)PdCl2] (0.202 g, 0.71 mmol) in dichloromethane (4-5
mL) was treated with a dichloromethane solution (5 mL) of
2-methyl-2-pyridin-2-yl-1,3-bis(diphenylphosphino)propane
(0.365 g, 0.725 mmol) and stirred vigorously for ca. 1-2 h. The
reaction mixture was filtered and the precipitate washed with
hexane (2 × 10 mL) and dried under vacuum to give 2a as a
yellow solid in 81% yield (0.392 g). Crystallization from a
pyridine solution layered with hexane gave X-ray quality
crystals of 2a . 31P{1H} NMR (121.4 MHz, C5D4N, δ): 19.0 (s,
PPh2). 1H NMR (300.0 MHz, CDCl3, δ): 8.23 (m, 4H, C6H5),
8.13 (dm, 1H, C6H5), 7.79 (m, 4H, C6H5), 7.28-7.04 (m, 13H,
C6H5), 6.87 (m, 1H, C6H5), 6.77 (m, 1H, C6H5), 3.10 (br m, 2H,
CH2), 2.82 (dd, J HH ) 14.9 Hz, 9.4 Hz, 2H, CH2), 0.83 (s, 3H,
CH3). Anal. Calcd for C33H31Cl2NP2Pd‚4C5H5N: C, 63.83; H,
5.15; N, 7.02. Found: C, 64.33; H, 5.43; N, 7.41.
Syn th esis of [{2-Meth yl-2-pyr idin -2-yl-1,3-bis(diph en yl-
p h osp h in o)p r op a n e}P d MeCl] (4a ). A dichloromethane so-
lution of [(cycloocta-1,5-diene)PdMeCl] (0.072 g, 0.27 mmol)
was treated with a dichloromethane solution of 2-methyl-2-
pyridin-2-yl-1,3-bis(diphenylphosphino)propane (0.137 g, 0.27
mmol) and stirred rapidly for ca. 2-3 h. The reaction mixture
was filtered and the residue washed with hexane (2 × 10 mL)
and crystallized from a dichloromethane solution layered with
hexane to give 4a as yellow crystals in 69% yield (0.122 g).
31P{1H} NMR (121.4 MHz, CDCl3, δ): 29.4 (d, 2J PP ) 48.6 Hz,
Compounds 2b-c were prepared according to the procedure
described above.
2
1
PPh2), -1.79 (d, J PP ) 48.6 Hz, PPh2). H NMR (300.0 MHz,
CD2Cl2, δ): 8.44 (m, 1H, C5H4N/C6H5)), 8.14 (m, 2H, C5H4N/
C6H5), 8.03 (m, 2H, C5H4N/C6H5), 7.72 (m 2H, C5H4N/C6H5),
7.62 (m 2H, C5H4N/C6H5), 7.58-7.52 (m 7H, C5H4N/C6H5), 7.44
Syn t h esis of [{2-Met h oxym et h yl-2-m et h yl-1,3-b is(d i-
p h en ylp h osp h in o)p r op a n e}P d Cl2}] (2b). Compound 2b
was isolated as a yellow solid in 80% yield (0.254 g) from a
dichloromethane solution layered with hexane. 31P{1H} NMR
2
2
(m, 6H, C5H4N/C6H5), 3.03 (dd, J HH ) 15.3 Hz, J PH, 6.3 Hz,
1
(121.4 MHz, CDCl3, δ): 18.0 (s, PPh2). H NMR (300.0 MHz,
2
2
1H, CHaCHb), 2.91 (dd, J HH ) 15.3 Hz, J PH ) 5.0 Hz, 1H,
CDCl3, δ): 7.88 (m, 4H, C6H5), 7.80 (m, 4H, C6H5), 7.40 (m,
12H C6H5), 2.60 (s, 3H, CH3), 2.50 (s, 2H, CH2), 2.40 (ABd,
J HH ) 15.3 Hz, 8.8 Hz, 2H, CH2), 2.18 (ABd, J HH ) 15.3 Hz,
CHcCHd), 2.82 (dd, J HH ) 2J PH ) 15.3 Hz, 1H, CHaCHb), 2.72
2
2
2
(dd, 1H, J HH ) J PH ) 15.3 Hz, CHcCHd), 0.94 (s, 3H, CH3),
3
0.57 (dd, J PH ) 7.8, 6.6 Hz, 3H, Pd-CH3). Anal. Calcd for
8.8 Hz, 2H, CH2), 0.60 (s, 3H, CH3). Anal. Calcd for C30H32
-
C
34H34ClNP2Pd‚CH2Cl2: C, 57.18; H, 4.87. Found: C, 57.44;
Cl2OP2Pd: C, 55.64; H, 4.98. Found: C, 55.91; H, 4.72.
H, 4.57.
Syn t h esis of [{2-Met h yl-2-p h en yl-1,3-b is(d ip h en yl-
p h osp h in o)p r op a n e}P d Cl2}] (2c). Compound 2c was pre-
pared according to the procedure described above and was
isolated as a pale yellow solid in 68% yield (0.277 g). 31P{1H}
Syn th esis of [{(S)-(+)-N,N-Dim eth yl-r-m eth ylben zyl-
a m in e-C,N}P d {MeOCH2}CMe{CH2P P h 2}2][ClO4] (5b). A
solution of (S)-(+)-bis(µ-chloro)bis[N,N-dimethyl-R-methyl-
benzylamine-C,N]dipalladium (0.78 g, 0.13 mmol) in dichloro-
methane (ca. 5 mL) and silver perchlorate (0.056 g, 0.26 mmol)
was stirred at room temperature in the dark for ca. 2 h. The
resulting cloudy reaction mixture was filtered and then treated
with a dichloromethane solution (5 mL) of 2-methoxymethyl-
2-methyl-1,3-bis(diphenylphosphino)propane (0.127 g, 0.27
mmol) and stirred for a further 1 h. The solvent was removed
to give 5b as an off-white solid in 70% yield (0.152 g).
Crystallization from warm methanol afforded X-ray quality
crystals of 5b, as a 1:1 mixture of diastereoisomers. 31P{1H}
NMR (121.4 MHz, CDCl3, δ): 29.0 (d, J PP ) 46.0 Hz), 28.6 (d,
J ) 46.0 Hz), 1.75 (d, J ) 46.0 Hz), 1.55 (d, J PP ) 46.0 Hz). 1H
NMR (300.0 MHz, CDCl3, δ): 8.2-6.4 (m, 24H, C6H5/C6H4),
3.75 (dq, J HH ) J PH ) 6.1 Hz, 1H, CHMe), 3.54 (dq, J HH ) J PH
) 6.1 Hz, 1H, CHMe), 2.93 (s, 3H, CH2OMe), 2.75 (s, 3H,
CH2OMe), 2.7-2.0 (m, 6H, PCH2/CH2OMe), 2.29 (d, J ) 1.6
Hz, 3H, NMe2), 2.27 (d, J ) 1.6 Hz, 3H, NMe2), 2.22 (s, 3H,
NMe2) 2.19 (s, 3H, NMe2), 1.74 (d, J ) 6.1 Hz, 3H, CHMe),
1.73 (d, J ) 6.1 Hz, 3H, CHMe), 0.61 (s, 3H, C(Me)CH2OMe),
0.38 (s, 3H, C(Me)CH2OMe). Anal. Calcd for C40H46ClNO5-
P2Pd: C, 58.28; H, 5.62. Found: C, 58.66; H, 5.73.
1
NMR (121.4 MHz, CDCl3, δ): 21.2 (s, PPh2). H NMR (300.0
MHz, CDCl3, δ): 7.79-6.78 (m, 25H, C6H5), 2.96 (dd, J HH
)
14.9 Hz, 9.4 Hz, 2H, CH2), 2.88 (dd, J HH ) 14.9 Hz, 9.4 Hz,
2H, CH2), 0.87 (s, 3H, CH3). Anal. Calcd for C34H33Cl2P2Pd:
C, 59.99; H, 4.89. Found: C, 60.23; H, 5.03.
Syn th esis of [{2-Meth yl-2-pyr idin -2-yl-1,3-bis(diph en yl-
p h osp h in o)p r op a n e}P d (OAc)2] (3a ). A suspension of pal-
ladium acetate (0.61 g, 2.98 mmol) in toluene (∼1-2 mL) was
treated with a toluene solution (∼5-6 mL) of 2-methyl-2-
pyridin-2-yl-1,3-bis(diphenylphosphino)propane (1.50 g, 2.98
mmol) and stirred vigorously for ca. 30 min, during which time
a pale-colored solid precipitated from solution. The reaction
mixture was filtered, and the precipitate was washed with
toluene (2 × 2 mL) and hexane (3 × 10 mL) and dried under
vacuum to give 3a as a salmon pink solid in 77% yield (1.62
g). 31P{1H} NMR (121.4 MHz, CDCl3, δ): 17.4 (s, PPh2). 1H
NMR (300.0 MHz, CDCl3, δ): 8.49 (m, 1H, C5H4N/C6H5), 7.94
(m, 4H, C5H4N/C6H5), 7.64 (m, 4H, C5H4N/C6H5), 7.45-7.15
(m, 13H, C5H4N/C6H5), 7.02 (m, 2H, C5H4N/C6H5), 3.09 (dd,
2H, J ) 7.9 Hz, 15.2 Hz, CH2), 2.39 (dd, 4H, J ) 8.9 Hz, 15.2
Hz, CH2), 1.43 (br s, 6H, O2CCH3), 1.27 (s, 3H, 2-py-CCH3).
P olym er iza tion P r oced u r e a n d P olym er Ch a r a cter -
iza tion . Polymerizations were conducted in methanol in a 300
mL autoclave. The catalyst precursors were prepared according
Compounds 3b-c were prepared according to the procedure
described above.