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V. Gomez-Benıtez et al. / Journal of Molecular Structure 689 (2004) 137–141
138
2. Experimental
2.1. Materials and methods
Table 1
Summary of crystal structure data for compound [RuCl2(CO)(DMF)(PPh3)2] (1)
Empirical formula
C40H37Cl2NO2P2Ru
Unless stated otherwise, all reactions were carried out
under an atmosphere of dinitrogen using conventional
Schlenk glassware. The IR spectra were recorded on a
Nicolet-Magna 750 FT-IR spectrometer as nujol mulls.
The 1H and 31P{1H} NMR spectra were recorded on a JEOL
GX300 spectrometer. Chemical shifts are reported in ppm
down field of TMS using the solvent (CDCl3, d ¼ 7:27) as
internal standard. 31P{1H} NMR spectra were recorded with
complete proton decoupling and are reported in ppm using
85% H3PO4 as external standard. Elemental analyses were
determined on a Perkin-Elmer 240. Positive-ion FAB mass
spectra were recorded on a JEOL JMS-SX102A mass
spectrometer operated at an accelerating voltage of 10 Kv.
Samples were desorbed from a nitrobenzyl alcohol (NOBA)
matrix using 3 KeV xenon atoms. Mass measurements in
FAB are performed at a resolution of 3000 using magnetic
field scans and the matrix ions as the reference material or,
alternatively, by electric field scans with the sample peak
bracketed by two (polyethylene glycol or cesium iodide)
reference ions. The N,N0-dimethylformamide (DMF) was
purchased from Aldrich Chemical Co. and used without
further purification. The complex [RuCl2(PPh3)3] [7] was
prepared according to published procedures.
Formula weight
Temperature
797.62
291(2) K
˚
Wavelength
0.71073 A
Triclinic
P 2 1
Crystal system
Space group
˚
Unit cell dimensions
a ¼ 11.7834(6) A, a ¼ 70.810(1)8
˚
b ¼ 12.7571(7) A, b ¼ 86.480(1)8
˚
c ¼ 13.3405(7) A, g ¼ 75.007(1)8
3
˚
Volume
1828.8(2) A
Z
2
Density (calculated)
Absorption coefficient
Fð000Þ
1.448 g/cm3
0.698 mm21
816
Crystal size
0.20 £ 0.14 £ 0.10 mm
1.75–25.008
u range for data
collection
Index ranges
213 # h # 14; 215 # k # 15; 215 # l # 15
15088
Reflections collected
Independent reflections
Absorption correction
Refinement method
Data/restraints/
parameters
6424 ½RðintÞ ¼ 0:0379ꢀ
None
Full-matrix least-squares on F2
6424/0/435
Goodness-of-fit on F2
Final R indices
½I . 2sðIÞꢀ
0.949a
R1 ¼ 0:0328; wR2 ¼ 0:0534a
R indices (all data)
Largest diff. peak
and hole
R1 ¼ 0:0458; wR2 ¼ 0:0551b
23
˚
0.622 and 20.378 e A
2.2. Synthesis of [RuCl2(CO)(DMF)(PPh3)2] (1)
a
2
2 2
S ¼ ½wðFoÞ 2 ðFcÞ Þ =ðn 2 pÞꢀ1=2 where n ¼ number of reflections and
p ¼ total number of parameters.
A solution [RuCl2(PPh3)3] (50 mg, 0.052 mmol) in
DMF (30 cm3) was set to reflux for 2.0 h. After the
prescribed time the resulting solution was evaporated in a
rotovapor and the yellow residue recrystallized from
CH2Cl2/Hexane to yield a microcrystalline yellow powder
of 1. Yield 39 mg (93%).
b
2
2
2
2 1=2
R1 ¼ lFo 2 Fcl=lFol; wR2 ¼ ½wððFoÞ 2 ðFcÞ Þ =wðFoÞ ꢀ
:
using SHELXS-97 [8] program. The remaining atoms were
located via a few cycles of least squares refinements and
difference Fourier maps, using the space group P 2 1;
with Z ¼ 2: Hydrogen atoms were input at calculated
positions, and allowed to ride on the atoms to which they are
attached. Thermal parameters were refined for hydrogen
2.3. Data Collection and refinement for
[RuCl2(CO)(DMF)(PPh3)2] (1)
˚
atoms on the phenyl groups using a Ueq ¼ 1.2 A to precedent
atom. The final cycle of refinement was carried out on all
non-zero data using SHELXL-97 [9] and anisotropic thermal
parameters for all non-hydrogen atoms. The details of the
structure determination are given in Table 1 and selected bond
A crystalline yellow prism of [RuCl2(CO)(DMF)(PPh3)2],
grown from a DMF saturated solution of 1 was glued to a glass
fiber. The X-ray intensity data were measured at 291 K on a
Bruker SMART APEX CCD-based X-ray diffractometer
system equipped with a Mo-target X-ray tube (l ¼
˚
lengths (A) and angles (8) in Table 2. The numbering of the
atoms is shown in Fig. 1 (ORTEP) [10].
˚
0.71073 A). The detector was placed at a distance of
4.837 cm. from the crystal. A total of 1800 frames were
collectedwithascanwidthof0.38 in v andanexposuretimeof
10 s/frame. The frames were integrated with the Bruker
SAINT software package using a narrow-frame integration
algorithm. The integration of the data using a triclinic unit cell
yielded a total of 15088 reflections to a maximum 2u angle of
3. Results and discussion
3.1. Synthesis of [RuCl2(CO)(DMF)(PPh3)2] (1)
˚
50.008 (0.93 A resolution), of which 6424 were independent
By setting to reflux a solution of [RuCl2(PPh3)3] in DMF
for 2.0 h. the product [RuCl2(CO)(DMF)(PPh3)2] (1) can be
isolated as a yellow microcrystalline powder in quantitative
yield. Infrared analysis of a sample of 1 affords a spectrum
(Rint ¼ 3:79%; Rsig ¼ 6:06%) and 4401 were greater than
2sðF2Þ: Analysis of the data showed negligible decay during
data collection. The structure was solved by Patterson method