Y. Kim, J.G. Verkade / Journal of Organometallic Chemistry 669 (2003) 32ꢀ
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33
2. Experimental
v-scans at different starting angles. Each series con-
sisted of 30 frames collected at intervals of 0.38 in a 108
range about v with an exposure time of 10 s per frame.
A total of 189 reflections were obtained. The reflections
were successfully indexed by an automated indexing
routine built into the SMART program. The final cell
constants were calculated from a set of 4352 strong
reflections from the actual data collection. The data
were collected using the full sphere routine. A total of
10 069 data were harvested by collecting four sets of
frames with 0.38 scans in v with an exposure time 10 s
per frame. This dataset was corrected for Lorentz and
polarization effects. The absorption correction was
based on a function fitted to the empirical transmission
surface as sampled by multiple equivalent measurements
[21] using SADABS software [22]. The compound crystal-
2.1. General considerations
All reactions were carried out under argon using
standard Schlenk and glove box techniques [18] and
chemicals were purchased from Aldrich and were used
as supplied unless otherwise indicated. THF and toluene
(Fisher HPLC grade) were dried and purified under
nitrogen in a Grubbs-type non-hazardous two-column
solvent purification system [19] (Innovative Technolo-
˚
gies) and were stored over activated 3 A molecular
sieves. All deuterium solvents were dried over activated
˚
molecular sieves (3 A) and were used after vacuum
transfer to a Schlenk tube equipped with J. Young valve.
1H, 13C{1H}- and 31P-NMR spectra were recorded at
ambient temperature on a Varian VXR-400 NMR
spectrometer using standard parameters. Chemical
shifts are referenced to the residual peaks of CDCl3
¯
lized in the triclinic system and the space group P1 was
/
confirmed [22]. The position of the heavy atom was
found by the Patterson method. The remaining atoms
were located in an alternating series of least-squares
cycles and difference Fourier maps. All non-hydrogen
atoms were refined in a full-matrix anisotropic approx-
imation. All hydrogen atoms were placed in the
structure factor calculation at idealized positions and
were allowed to ride on the neighboring atoms with
relative isotropic displacement coefficients. Final least-
squares refinement of 253 parameters against 4877
independent reflections converged to an R (based on
1
(7.24 ppm, H-NMR; 77.0 ppm, 13C{1H}-NMR). Ele-
mental analysis was performed by Desert Analytics
Laboratory.
2.2. Synthesis
PdCl2(PhCN)2 [20] and 2 [13] were synthesized by
literature procedures and 4 was synthesized as follows.
To a solution of PdCl2(PhCN)2 (500 mg, 1.31 mmol) in
30 ml of toluene was added a solution of 2 (617 mg, 1.31
mmol) in 20 ml of toluene at room temperature (r.t.)
under an atmosphere of Ar. The reaction mixture was
stirred for 12 h after which the volatiles were removed
under reduced pressure to yield a yellow solid, which
F for I ]
/
2s) and a wR (based on F for I ]2s) of
/
0.0255 and 0.0587, respectively. The detailed data are
given in Table 1.
was recrystallized from THFꢀ
(0.74 g, 75%).
1H-NMR (CDCl3, 400.147 MHz): d 5.96 (d, Jꢂ
Hz, 3H, CHP), 3.74 (m, 4H, CH2O), 1.84 (m, 4H,
CH2CH2O).
13C{1H}-NMR (CDCl3, 100.626 MHz): d 85.9 (d,
/
ether in a refrigerator
3. Results and discussion
/
6.7
Ligand 2 was easily synthesized by a modification of a
literature method whose last step is the reaction of
P[CH(CCl3)OH]3 with PCl3 in THF, giving a 32% yield
[13]. We used P(OMe)3, which in our hands worked
more conveniently than PCl3, although the yield (ca.
30%) was similar. Compound 2 was purified before use
by sublimation per 70 8C per 7 mm. When ligand 2 was
allowed to react with one equivalent of PdCl2(PhCN)2
(Scheme 1) a yellow powder 3 was obtained in 86% yield
Jꢂ
(OCH2), 25.6 (OCH2CH2).
31P-NMR (CDCl3, 81.01 MHz): d 77.7 (br, PO),
/
7.8 Hz, PCH), 85.4 (d, Jꢂ8.1 Hz, CCl3), 68.1
/
ꢃ
/
13.2 (d, Jꢂ
Elemental
/
12.2 Hz, PCH).
analysis:
Anal.
Calc.
for
1
C10H11Cl11P2O4Pd: C, 15.94; H, 1.47; P, 8.22. Found:
C, 15.88; H, 1.71; P, 7.86%.
after evaporation. According to its H-NMR spectrum,
this complex contains a coordinated PhCN molecule.
However, recrystallization from THFꢀdiethyl ether
/
2.3. X-ray structure determination
caused the replacement of the PhCN by THF, affording
4 in 75% yield. Complex 4 is soluble in polar organic
solvents and in toluene, but it is insoluble in alkanes
such as n-hexane. In the solid state, 4 is air-stable for
extended periods and is also quite thermally stable,
resisting decomposition, even upon heating to 100 8C
under vacuum.
A yellow single crystal selected under ambient condi-
tions was mounted and centered in the X-ray beam by
using a video camera. The crystal evaluation and data
collection were performed at 173 K on a Bruker CCD-
˚
Ka (lꢂ0.71073 A) radia-
1000 diffractometer with Moꢀ
/
/
tion with a detector-to-crystal distance of 5.03 cm. The
initial cell constants were obtained from three series of
The composition of 4 was established by 1H-,
13C{1H}- and 31P-NMR spectroscopy and by elemental
Kim, Youngjo
