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E. Lozano Diz et al. / Polyhedron 20 (2001) 2771–2780
the solvent was removed under vacuum. The resulting
dark-red residue was dissolved in a minimum amount
(ca. 5 ml) of CH2Cl2. The product (1) was isolated by
preparative thin-layer chromatography of this solution
(silica gel 60 GF254, Merck), using cyclohexane–CH2Cl2
(5:1) as eluent, from the main red band. Crystallisation
from dichloromethane gave 1 in 77% yield.
tion system (Stoe & Cie, 1995) using Mo Ka graphite
monochromated radiation; the imaging plate distance
was 90 mm, b oscillation scans 0–180°, step Db=0.5°,
,
2q range 2.54–45.0°, dmax−dmin=16.00−0.93 A. For
2, imaging plate distance was 90 mm, b oscillation
scans 0–184°, step Db=0.5°, 2q range 2.54–45.0°,
,
max−dmin=16.00−0.93 A. For 3 and 4, data collec-
d
tion was performed at 153 K using Mo Ka radiation
,
3.2. Synthesis of Ru3(CO)10(F-dppe) (2) and
Ru3(CO)8(F-dppe)2 (4)
(u=0.71073 A), 200 exposures (3 min per exposure),
imaging plate distance 70 mm, b oscillation scans
,
0–200°, step Db=1°, dmax−dmin=12.445−0.81 A.
A solution of Ru3(CO)12 (150 mg, 0.24 mmol) in thf
(30 ml) was treated with F-dppe (179 mg, 0.24 mmol
(for 2 as major product); 537 mg, 0.72 mmol (for 4 as
major product)) and refluxed under vigorous stirring.
The solution colour changed from orange to red. The
reaction was monitored by FT-IR and stopped when
the characteristic Ru3(CO)12 absorption at w=2061
cm−1 disappeared; this was the case after 16 h of
reflux. Then the solvent was removed under vacuum.
The resulting orange–red residue was dissolved in a
minimum amount (ca. 5 ml) of CH2Cl2. Preparative
thin-layer chromatography of this solution (silica gel 60
GF254, Merck) using cyclohexane/CH2Cl2 (1:1) as elu-
ent, gave unreacted Ru3(CO)12 (1%) as the first yellow
band. The products were extracted from the second red
band (2) and from the third red band (4) with CH2Cl2
and recrystallised from dichloromethane for 2 and
dichloromethane/methanol (9:1) for 4. Yields: (2) 36%;
(4) 32%. Anal. Found: C, 32.28; H 0.16. Calc. for
C36H4O10F20P2Ru3 (2): C, 32.23; H, 0.3%. Anal. Found:
C, 35.07; H, 0.58. Calc. for C60H8F40P4Ru3 (4): C,
35.26; H, 0.39%.
Alternati6e preparation of 3: Sodium diphenylketyl
was prepared as described bellow [14], then a solution
of Ru3(CO)12 (100 mg, 0.15 mmol) in thf (30 ml) was
treated with F-dppe (224 mg, 0.30mmol) and heated at
40 °C. Then five drops of the sodium diphenylketyl
solution were added and the stirring of the solution at
40 °C was continued until the characteristic Ru3(CO)12
absorption at w=2061 cm−1 had disappeared; this was
the case after 25 min. The solution was filtered (unre-
acted F-dppe) and then, the solvent was removed under
vacuum. The resulting dark-red residue was dissolved in
a minimum amount (ca. 5 ml) of CH2Cl2. The product
(3) was isolated by preparative thin-layer chromatogra-
phy of this solution (silica gel 60 GF254, Merck), using
cyclohexane/CH2Cl2 (4:1) as eluent, from the main red
band. Crystallisation from dichloromethane gave 3 in
79% yield.
All structures were solved by direct methods using the
programme SHELXS-97 [20]. The refinement and all
further calculations were carried out using SHELXL-97
[21]. The H atoms were included in calculated positions
Table 7
Crystal data and structure refinement parameters for 1 and 2
1
2
Empirical
C35H42O10P2Ru3
C
36H4F20O10P2Ru3
formula
·1/2(CH2Cl2)
1384.00
triclinic
rod
Formula weight
Crystal system
Crystal shape
Crystal colour
Space group
Unit cell
987.84
orthorhombic
block
orange
Pca21
red
(
P1
dimensions
,
a (A)
27.1737(12)
11.0849(6)
52.721(3)
90
90
90
15880.5(14)
16
1.653
13.1110(10)
17.7259(12)
20.8427(15)
71.947(8)
79.706(9)
71.491(8)
4349.9(5)
4
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
V (A )
3
,
Z
Dcalc (g cm−3
)
2.113
Absorption coefficient
(mm−1
F(000)
1.259
1.305
)
7904
2652
Crystal size (mm)
Angle range
Index ranges
0.45×0.45×0.25
2.29BqB25.77
−235h528,
−105k511,
−565l555
21 638
14 561
15 546
0.0309
0.35×0.20×0.10
2.02BqB25.91
−165h516,
−215k521,
−255l524
31 507
11 602
15 720
0.023
Reflections measured
Reflections observed
Independent reflections
Rint
Radiation used
R1 [I\2|(I)],
R1 (all data) a
wR2 [I\2|(I)],
wR2 (all data) b
Goodness-of-fit
on F2 c
Mo Ka
Mo Ka
0.0243, 0.0270
0.0222, 0.0381
0.0579, 0.0590
0.973
0.0442, 0.0466
0.820
3.3. Crystallography
a R1=ꢀ(ꢁFoꢁ−ꢁFcꢁ)/ꢀꢁFoꢁ.
b wR2=[ꢀw(Fo2−Fc2)2/ꢀ(Fo2)4]1/2
.
Suitable crystals of 1–3 were grown from CH2Cl2
and 4 from CH2Cl2/MeOH (9:1). For 1, intensity data
were collected at 153 K on a Stoe image plate diffrac-
c S=[ꢀw(F2o−Fc2)2/(n−p)]1/2 (n=number of reflections, p=num-
ber of parameters), calc. w=1/[|2(Fo2)1(0.0431P)2+0.0000P] where
P=(F2o+2F2c)/3.
Diz, Enrique Lozano
