R.-X. Li et al. / Journal of Organometallic Chemistry 557 (1998) 207–212
209
Table 2
peaks were presented in Tables 1 and 2 gave selected
bond distances and angles.
Selected bond lengths and angles for RuH2(CO)(PPh3)(BISBI)
˚
Bond
Lengths (A) or angles(°)
Ru–C(1)
Ru–P(1)
Ru–P(2)
Ru–P(3)
1.88 (1)
2.33 (1)
2.30 (1)
2.38 (1)
1.15 (1)
106.6(1)
96.0(1)
144.5(1)
91.7(1)
101.1(1)
105.4(1)
4. Results and discussion
4.1. Complex 1
C(1)–O
The green solid complex was quite stable in air, but
it was very unstable in solution when exposed in air,
and the color of solution quickly changed from yellow-
brown to brown and unidentified black precipitate was
formed. When the complex was dissolved in organic
solvents, such as, benzene and CHCl3 under nitrogen,
the color of solutions were brown, not green. The
carbon and hydrogen analysis of the green product was
consistent with the formula RuCl2(PPh3)(BISBI).
31P{1H}-NMR spectra in CDCl3 or C6D6 exhibited two
doublets at 54.8 and 52.9 ppm with coupling constant
C(1)–Ru–P(1)
C(1)–Ru–P(2)
P(1)–Ru–P(2)
C(1)–Ru–P(3)
P(1)–Ru–P(3)
P(2)–Ru–P(3)
(t), JP–Pcis=18 Hz, JP–Ptrans=296 Hz; 48.4 (dd), 32.8
(dd), and 27.2 (t), JP–Pcis=13 Hz, JP–Ptrans=296 Hz;
1H-NMR: l (ppm) −6.95 (dt), JH–Pcis=31 Hz, and
JH–Ptrans=108 Hz. IR: wCO=1930 cm−1 (vs), wRu–H
=
2038 cm−1 (w).
J
PP=44 Hz and a strong singlet at −6.7 ppm. The
former was a typical AB splitting pattern of dimer
ruthenium-phosphine complexes with chloride bridges
[5,26], and the latter was assigned to free PPh3. The
integration ratio of two doublets to singlet was roughly
2. Moreover, except for the two doublets and the
singlet of free PPh3 in this solution, any peaks of 1
could not be observed on the spectra.
However, besides of the two doublets of dimer and
the singlet of free PPh3, the 31P-NMR spectra appeared
two very weak wide doublets at 13.2 and 47.2 ppm and
a wide singlet at 71.2 ppm at −20.0°C. When the
temperature was further decreased to −55°C, the in-
tensities of the three new wide peaks were greatly
increased and sharpened, the 31P{1H}-NMR spectra
clearly exhibited two doublets of doublet at 13.2 and
47.2 ppm and a unsymmetric quartet at 71.2 ppm.
Their coupling constants were JPx–Pa=20 Hz and JPb–
3.3. RuH2(CO)(PPh3)(BISBI) 3
It was synthesized by the same method as in complex
2, but RuH2(CO)(PPh3)3 0.18 g (0.2 mmol) and BISBI
0.11 g (0.2 mmol) were used as the starting materials.
Pale yellow microcrystals were obtained with 0.12 g
(65%) yield. Anal.: Calc. for C57H49OP3Ru: C, 72.52%,
H, 5.23%; Found: C, 72.08%, H, 5.10%. 31P{1H}NMR:
l (ppm) 58.9 (dd), 56.1 (dd) and 55.3 (t), JP–Pcis=14
1
Hz, JP–Ptrans=232 Hz; H-NMR: l (ppm) −7.9 (m, 1
H), JHa–Pcis=17 and 18 Hz, JHa–Hb=8.1 Hz; −9.5
(ds, 1 H), JHb–Pcis=33 Hz, JHb–Ptrans=71 Hz. IR,
wCO=1939 cm−1 (vs).
3.4. X-ray crystallographic analysis of 3
Pa=306 Hz at 13.2 ppm, JPx–Pb=38 Hz and JPa–Pb
308 Hz at 47.2 ppm, and Pa–Px=20 Hz and
Pb–Px=38 Hz at 71.2 ppm. This result confirmed that
=
The crystal used for X-ray diffraction were grown
from a 2:1 mixture solvent of toluene and n-hexane.
The colorless plate crystal (0.22×0.22×0.25 mm) was
covered with a thin layer of paraffin oil as a precaution
against decomposition in air, and was mounted on a
Rigaku RAXIS IIC imaging-plate diffractometer. In-
tensity data were collected at 293 K using graphite-
J
J
complex 1 was only stable in solution at very low
temperature. However, the peak intensity of the AB
splitting pattern of dimer was still greater than the new
ABX splitting pattern (the ratio was about 2:1) at
−55°C. Furthermore, when the equil molar ratio PPh3
was dissolved in the CDCl3 solution of 1, the color of
solution changed from brown to green-yellow, the sin-
glet peak of PPh3 was enhanced, two doublets at 54.8
and 52.9 ppm were not remarkable change, but three
very weak wide peaks with ABX splitting pattern were
appeared at 13.0, 47.2 and 71.2 ppm. Attempts to
isolate the dimer complex from its oganic solution by
adding diethyl ether or n-hexane were unsuccessful,
only the original green solid complex 1 was recovered.
These results suggested that PPh3 in the complex was
almost completely dissociated in organic solvent and
˚
monochromatized Mo Kh (u=0.71073 A) radiation
from a rotating-anode generator operating at 50 kV
and 90 mA. The q range for data collection was 1.58–
26.74°, 45° oscillation frames was in the range 0–135°,
and the exposure was 10 min. per frame. A self-consis-
tent semi-empirical absorption correction was applied
by using the ABSCOR program. All calculation were
performed with Siemens SHELXTL PLUS (PC Version)
system. Structure refinement was based on F2 for all
10601 reflections. A final R-factor is 0.0690, wR 0.1664,
the largest and mean D/|, and the largest difference