N. Nawar / Journal of Organometallic Chemistry 605 (2000) 1–6
5
3.6.2. Crystal structure analysis of
[(C5H5)Ru(v-CO)2(v-Ph2PN(H)PPh2}IrCl2] (6)
Crystals of complex were grown from
3.4. Preparation of [(C5H5)RuCl{(PPh2)2CH-
CH2PPh2}Ir(CO)2Cl] (8)
6
a
dichloromethane/heptane solution. A suitable yellow
prism crystal of dimensions 0.35×0.15×0.30 mm was
mounted on a glass fiber. The data were collected at
temperature of −12091°C. Cell constants and an
orientation matrix for data collection were obtained
from a least-squares refinements using the setting angles
of 20 carefully centered reflections in the range 34.9B
2qB41.33°. A total of 12 404 reflections recorded, of
which 11 924 unique (q=25°, Rint=0.069) using the ꢀ
scan technique. The intensities of three representative
reflections, which were measured after every 150 reflec-
tions, remained constant throughout data collection
indicating crystal and electronic stability (no decay
correction was applied). The final cycle of full-matrix
least-squares refinement was based on 5684 observed
reflections (I\3|(I)) and 527 variable parameters. The
weighting scheme was w=4F2o/|2(Fo)2. The final R and
R% values were 0.042 and 0.045, respectively.
A
freshly prepared solution of [Ru(C5H5)Cl-
{(PPh2)2CHCH2PPh2}] [17] (0.058 g, 0.074 mmol) in
THF (10 ml) was added to a solution of [IrCl-
(CO)2(p-toluidine)] (0.028 g, 0.074 mmol) in THF (10
ml). The mixture was stirred at 50°C and after 10 min,
the solution was evaporated to dryness. The remaining
solid was recrystallized from THF/benzene to give
complex 8 as a yellow solid (0.059 g, 73.6%). Anal.
Found: C, 50.15; H, 3.25. Calc. for C45H38Cl2IrO2P3Ru:
C, 50.6; H, 3.6%.
3.5. Preparation of
[(C5H5)Ru¸(v¹-¹C¹O¹){¹(P¹P¹h¹2¹)2¹C¹H¹C¹H¹2P¹P¹h¹2º}IrCl2] (9)
Complex 8 (0.03 g, 0.028 mmol) was dissolved in
THF (20 ml) and stirred at 40°C for 48 h. 31P-NMR
spectroscopy showed the reaction had occurred. Alter-
natively, complex 9 was prepared by the dropwise
addition of Me3NO·2H2O (0.003 g, 0.028 mmol) in
methanol (2 ml) to a solution of complex 8 in THF (20
ml) with constant stirring. Spectroscopic analyses
showed that complete conversion to complex 9 had
occurred. The yellowish–brown solution was evapo-
rated to dryness, and was recrystallized from THF/ben-
zene to give complex 9 as a yellow solid (0.016 g,
51.3%). Anal. Found: C, 50.85; H, 3.45. Calc. for
C44H38Cl2IrOP3Ru: C, 50.82; H, 3.68%.
3.6.3. Crystal data
C31H26Cl2IrNO2P2Ru, M=870.7, monoclinic, space
group P21/n (no. 14), a=20.91(2), b=14.29(1), c=
3
,
,
24.13(1) A, i=106.52(7)°, V=6912(8) A (by least-
squares refinement of angles from 20 reflections),
,
Mo–Ka (u=0.71069 A) radiation, Z=8, Dcalc=1.80 g
cm−3, F(000)=3648, v=45.42 cm−1, T= −120°C,
R=0.042 (for 5684 reflections with I\3|(I)).
Acknowledgements
3.6. X-ray crystallography
We thank Professor A.K. Smith (CPE Lyon, France)
for collecting the X-ray data.
3.6.1. General information
Yellow crystals of the heterobimetallic complex
[(C5H5)Ru(m-CO)2(m-Ph2PN(H)PPh2}IrCl2] (6), suitable
for X-ray diffraction studies, were obtained. All mea-
surements were made on a Rigaku AFC6S diffractome-
ter equipped with graphite monochromated Mo–Ka
radiation. The basic crystallographic procedures used
have been fully described elsewhere [25,26]. An empiri-
cal absorption correction based on azimuthal scans was
applied. The data were corrected for Lorentz and polar-
ization effects. The structure was solved by direct meth-
ods. The non-hydrogen atoms were refined either
anisotropically or isotropically. Hydrogen atoms were
included in the structure factor calculation in idealized
position, and were assigned isotropic thermal parame-
ters, which were 20% greater than the Beq. value of the
atom to which they were bonded. All calculations were
performed using the TEXSAN crystallographic software
package supplied by the Molecular Structure Corpora-
tion [27].
References
[1] B.L. Shaw, M.J. Smith, G.N. Stretton, M. Thornton-Pett, J.
Chem. Soc. Dalton Trans. (1988) 2099.
[2] B. Chaudret, B. Delavaux, F. Dahan, R. Poilblanc,
Organometallics 4 (1985) 935.
[3] G.B. Jacobsen, B.L. Shaw, M. Thornton-Pett, J. Chem. Soc.
Chem. Commun. (1986) 13.
[4] R.H. Dawson, A.K. Smith, J. Organomet. Chem. 309 (1986)
C56.
[5] R.H. Dawson, A.K. Smith, J. Organomet. Chem. Chem. Com-
mun. (1987) 826.
[6] G.S. Ashby, M.I. Bruce, I.B. Tompkins, R.C. Wallis, Aust. J.
Chem. 32 (1979) 1003.
[7] C.S. Browning, D.H. Farrar, J. Chem Soc. Dalton Trans. (1995)
521.
[8] P. Braunstein, C. de Me´ric de Bellefon, B. Oswald, Inorg. Chem.
32 (1993) 1649.
[9] I. Bachert, I. Bartusseck, P. Braunstein, E. Guillon, J. Rose, G.
Kickelbick, J. Organomet. Chem. 580 (1999) 257.
Nawar, Nagwa
