48
J. Andrieu et al. / Journal of Organometallic Chemistry 601 (2000) 43–50
31P{1H}-NMR spectra were recorded at 300.13 and
121.5 MHz on a FT Bruker AC300 instrument and IR
spectra in the 4000–400 cm−1 range on a Bruker IFS66
FT spectrometer. The ligands Ph2PCH2C(O)Ph [2] and
Ph2PCH2C(O)NPh2 [3] and the complex [PdMe(Cl)-
(COD)] [46] were prepared according to literature pro-
cedures.
(m, 35H, phenyl). 31P{1H}-NMR (CD2Cl2): AB spin
system: lA 24.3, lB 27.6 (2JPP=391 Hz), −143.6 (sept.,
1
1P, PF−6 , JPF=714 Hz).
5.4. [Pd(SMe2)4](PF6)2 (4)
Pure dimethylsulfide (5 ml) was added to a solution of
Pd(OAc)2 (0.500 g, 2.23 mmol) in CH2Cl2 (10 ml).
Within a few seconds the solution went from brown to
yellow and after 5 min of stirring excess HPF6 (1 ml,
75% in H2O, 9.95 mmol) was added. After 30 min the
yellow precipitate formed was isolated, washed with
Et2O (3×15 ml) and THF (2×15 ml), and dried in
¸¹¹¹¹¹¹¹¹¹¹º
5.1. [PdMe{Ph2PCH2C(O)Ph}(PPh3)](PF6) (1)
A mixture of [PdMe(Cl)(COD)] (0.400 g, 1.50 mmol),
I (0.458 g, 1.50 mmol) and PPh3 (0.396 g, 1.50 mmol)
was stirred in CH2Cl2 (30 ml) for 1 h. Solid TlPF6 (0.492
g, 1.50 mmol) was added and the mixture was stirred
again overnight. The suspension was then filtered over
Celite and the pale yellow solution was concentrated in
vacuo. Addition of Et2O afforded colorless crystals,
which were filtered, washed with Et2O, and dried in
vacuo, yield: 1.070
g
(75%). Anal. Calc. for
C8H24F12P2PdS4: C, 14.90; H, 3.75. Found: C, 14.55; H,
1
3.63%. H-NMR (acetone-d6): l 2.65 (s, S(CH3)2).
¸¹¹¹¹¹¹¹¹¹¹º
(
5.5. [Pd{Ph2PCH···C(···O)Ph}(SMe2)2](PF6) (5)
vacuo, yield: 1.12
g
(90%). Anal. Calc. for
C39H35F6OP3Pd.0.5CH2Cl2: C, 54.16; H, 4.13. Found:
C, 54.25; H, 4.21%. IR (CH2Cl2): 1608 (s), 1593 (s), 1583
(w), 1575 (s), wCꢁO=1558 (s) cm−1. 1H-NMR (CD2Cl2):
l 0.91 (t, 3H, 3JPH=5.8 Hz, CH3), 4.61 (dd, 2H,
¸I¹n¹¹2¹0¹¹m¹l¹¹o¹f ºTHF were mixed together cis-
(
[Pd{Ph2PCH···C(···O)Ph}2 (0.230 g, 0.32 mmol) and
[Pd(SMe2)4](PF6)2 (0.207 g, 0.32 mmol). After stirring
for 5 h the solution was filtered over Celite, and the
solvent was removed in vacuo. The orange powder was
washed with a 1:1 mixture of Et2O–pentane (2×10 ml)
and dried in vacuo. Anal. Calc. for C24H28F6OP2PdS2:
C, 42.46; H, 4.16. Found: C, 42.39; H, 4.20%. IR
4
2JPH=6.1, JPH=2.6 Hz, PCH2), 7.82–6.50 (m, 30H,
phenyl). 31P{1H}-NMR (CD2Cl2): AB spin system: lA
25.4, lB 28.7 (2JPP=385 Hz), −143.7 (sept., 1P, PF−6 ,
1JPF=713 Hz).
(CH2Cl2): w(C···O)+w(C···C)=1510 cm−1 1H-NMR
.
¸¹¹¹¹¹¹¹¹¹¹º
5.2. [PdMe{Ph2PCH2C(O)Ph}(PCy3)](PF6) (2)
(acetone-d6): l 2.45 (s, 6H, S(CH3)2), 2.60 (s, 6H,
2
S(CH3)2), 5.05 (d, 1H, JPH=4.9 Hz, PCH), 7.40–8.00
Following the procedure described for 1, but starting
from [PdMe(Cl)(COD)] (0.335 g, 1.26 mmol), I (0.384 g,
1.26 mmol), PCy3 (0.354 g, 1.26 mmol) and TlPF6 (0.412
g, 1.26 mmol), 2 was obtained after crystallization from
a 1:3 mixture of CH2Cl2–Et2O as white crystals, yield:
0.998 g (93%). Anal. Calc. for C39H53F6OP3Pd: C,
55.03; H, 6.26. Found: C, 54.81; H, 6.25%. IR (CH2Cl2):
(m, 15H, phenyl). 31P{1H}-NMR (acetone-d6): l 43.0
(s).
5.6. Crystallographic analyses
The crystals used for the diffraction measurements
were mounted in thin-walled glass capillaries. Diffrac-
tion measurements were made on a Rigaku AFC6S fully
automated four-circle diffractometer. The unit cell was
determined and refined from 15 randomly selected
reflections, obtained by using the AFC6 automatic
search, center, index, and least-squares routines. Crystal
data, data collection parameters, and results of the
analyses are listed in Table 5. All data processing was
performed on a Digital Equipment Corp. Vaxstation
3520 by using the TEXSAN structure solving program
library obtained from the Molecular Structure Corp.,
The Woodlands, TX. Neutral atom scattering factors
were calculated by the standard procedures [47a].
Anomalous dispersion corrections were applied to all
non-hydrogen atoms [47b]. Lorentz/polarization (Lp)
and absorption corrections (based on three azimutal psi
scans) were applied to the data. Full-matrix least-
1
1609 (s), 1593 (s), 1575 (s) 1558 (s) cm−1. H-NMR
3
(CDCl3): l 0.80 (t, 3H, JPH=5.5 Hz, CH3), 1.30–2.00
(m, 33H, cyclohexyl), 4.65 (d, 2H, 2JPH=10.8 Hz,
PCH2), 7.30–8.15 (m, 15H, phenyl). 31P{1H}-NMR
(CDCl3): AB spin system: lA 24.9, lB 33.8 (2JPP=365
1
Hz), −143.6 (sept., 1P, PF−6 , JPF=711 Hz).
¸¹¹¹¹¹¹¹¹¹¹º
5.3. [PdMe{Ph2PCH2C(O)NPh2}(PPh3)](PF6) (3)
Following the procedure described for 1, but starting
from [PdMe(Cl)(COD)] (0.300 g, 1.13 mmol), II (0.447
g, 1.13 mmol), PPh3 (0.297 g, 1.13 mmol) and TlPF6
(0.395 g, 1.13 mmol), 3 was obtained after crystalliza-
tion from a 1:3 mixture of CH2Cl2–Et2O as white
needles, yield: 0.880
g (78%). Anal. Calc. for
C51H45F6NOP3Pd·1.25CH2Cl2: C, 56.67; H, 4.32; N,
1
1.27. Found: C, 56.63; H, 4.63; N, 1.44%. H-NMR
squares
refinements
minimized
the
function:
(CD2Cl2): l 0.65 (dd, 3H, 3JPH=5.9, 5.0 Hz, CH3), 3.80
ꢀ
hklw(ꢁFoꢁ−ꢁFcꢁ)2, where w=1/|(F)2, |(F)=|(Fo2)/2Fo
2
4
(dd, 2H, JPH=6.2, JPH=2.1 Hz, PCH2), 7.60–7.00
and |(F2o)=[|(Iraw)2+(0.02Inet)2]1/2/Lp.