+
+
Ruthenium and Osmium Aryls
Organometallics, Vol. 15, No. 20, 1996 4151
Ta ble 5. Cr ysta l, Da ta Collection , a n d Refin em en t
P a r a m eter s for
vibrating-sample magnetometer fitted with a Walker Scientific
magnet. Microanalyses (C, H, N) were done by using a Perkin-
Elmer 240C elemental analyzer. Electrochemical measure-
ments were performed under nitrogen atmosphere on a PAR
370-4 electrochemistry system as reported earlier.17 All
potentials reported in this work are uncorrected for junction
contribution. Solution (∼10-3 M) electrical conductivities were
measured with the help of a Philips PR 9500 bridge.
P r ep a r a tion of Com p lexes. The acetates M(η1-RL)-
(PPh3)2(CO)(η2-MeCO2) were synthesized by reacting M(η2-RL)-
(PPh3)2(CO)X with NaMeCO2‚3H2O. The benzoates M(η1-
RL)(PPh3)2(CO)(η2-PhCO2) were similarly prepared using
NaPhCO2. Yields were generally 80-85% on the basis of M(η2-
RL)(PPh3)2(CO)X for M ) Ru and 50-60% for M ) Os. Details
are given for representative cases.
Ca r bon yl(a ceta to)[4-m eth yl-6-(N-p -tolylim in om eth yl)-
p h en ol-C2]bis(tr ip h en ylp h osp h in e)r u th en iu m (II), Ru (η1-
MeC6H4L)(P P h 3)2(CO)(η2-MeCO2). To a vigorously stirring
solution of Ru(η2-MeC6H4L)(PPh3)2(CO)Cl (50 mg, 0.05 mmol)
in dichloromethane (20 mL) and acetone (20 mL) was added
dropwise an aqueous solution of NaMeCO2‚3H2O (50 mg, 0.35
mmol). The mixture was stirred until the original violet color
became yellow. The organic solvents were then removed under
reduced pressure leaving an aqueous suspension of a yellow
residue, which was isolated by filtration, washed repeatedly
Ru (η1-MeC6H4L)(P P h 3)2(CO)(η2-MeCO2) a n d
Ru (η1-MeC6H4L)(P P h 3)2(CO)(η2-P h CO2)‚C6H6
Ru(η1-MeC6H6H4L)-
Ru(η1-MeC6H4L)-
(PPh3)2(CO)(η2-PhCO2)‚
(PPh3)2(CO)(η2-MeCO2)
C6H6
mol formula
mol wt
cryst syst
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
C54H47NO4P2Ru
936.9
triclinic
P1h
11.079(2)
12.349(5)
18.486(8)
96.99(4)
94.10(3)
101.82(3)
2445(1.6)
2
C65H55NO4P2Ru
1077.1
triclinic
P1h
13.308(9)
14.638(8)
15.446(9)
100.61(5)
113.86(4)
90.94(5)
2691(2.5)
2
Z
D
calcd, g cm-3
1.273
1.329
temp, °C
radiation
22
22
Mo KR (graphite
monochromated)
0.710 73
ω
4.32
0.8262-0.9063
4.81
Mo KR (graphite
monochromated)
0.710 72
ω
4.01
0.8052-0.9122
6.44
λ, Å
scan technique
µ, cm-1
transm coeff
R,a
%
with water, and dried in vacuo. Anal. Calcd for RuC54H47
-
R,b %
5.09
1.04
6.65
1.30
NO4P2: C, 69.19; H, 5.06; N, 1.49. Found: C, 69.12; H, 5.08;
N, 1.57.
The complex Ru(η1-PhL)(PPh3)2(CO)(η2-MeCO2) was simi-
larly prepared. Anal. Calcd for RuC53H45NO4P2: C, 68.95; H,
4.92; N, 1.52. Found: C, 69.01; H, 4.89; N, 1.47.
GOFc
a
b
2
R ) ∑||Fo| - |Fc||/∑|Fo|. Rw ) [∑w(||Fo| - |Fc|)2/∑w|Fo| ]1/2
;
w-1 ) σ2|Fo| + g|Fo| ; g ) 0.0005. c The goodness of fit is defined
as [∑w(|Fo| - |Fc|)2/(no - nv)]1/2, where no and nv denote the
numbers of data and variables, respectively.
2
Ca r bon yl(ben zoa to)[4-m eth yl-6-(N-p -tolylim in om eth -
yl)p h en ol-C2]bis(tr ip h en ylp h osp h in e)r u th en iu m (II), Ru -
(η1-MeC6H4L)(P P h 3)2(CO)(η2-P h CO2). This complex was
prepared by the same procedure as above using NaPhCO2 in
place of NaMeCO2‚3H2O. Anal. Calcd for RuC59H49NO4P2: C,
70.91; H, 4.95; N, 1.40. Found: C, 70.85; H, 4.85; N, 1.47.
The complex Ru(η1-PhL)(PPh3)2(CO)(η2-PhCO2) was simi-
larly prepared. Anal. Calcd for RuC58H47NO4P2: C, 70.70; H,
4.81; N, 1.42. Found: C, 70.75; H, 4.88; N, 1.47.
Car bon yl(acetato)[4-m eth yl-6-(N-ph en ylim in om eth yl)-
p h en ol-C2]b is(t r ip h en ylp h osp h in e)osm iu m (II), Os(η1-
P h L)(P P h 3)2(CO)(η2-MeCO2). To a solution of Os(η2-PhL)-
(PPh3)2(CO)Br (50 mg, 0.05 mmol) in dichloromethane (20 mL)
and acetone (20 mL) was added an aqueous solution (10 mL)
of NaMeCO2‚3H2O (200 mg, 1.4 mmol). The reaction mixture
was then heated to reflux (6-7 h) until the violet solution
turned yellow. The organic solvents were removed under
reduced pressure. The aqueous suspension of the yellow
residue was filtered out, washed repeatedly with water, and
dried in vacuo. The yield was 60% on the basis of the bromo
precursor. Anal. Calcd for OsC53H45NO4P2: C, 62.87; H, 4.48;
N, 1.38. Found: C, 62.80; H, 4.52; N, 1.34.
Ca r bon yl(ben zoa to)[4-m eth yl-6-(N-p h en ylim in om eth -
yl)p h en ol-C2]bis(tr ip h en ylp h osp h in e)osm iu m (II), Os(η1-
P h L)(P P h 3)2(CO)(η2-P h CO2). This complex was prepared by
the same procedure as above using NaPhCO2 in place of
NaMeCO2‚3H2O. Anal. Calcd for OsC58H47NO4P2: C, 64.83;
H, 4.41; N, 1.30. Found: C, 64.89; H, 4.44; N, 1.23.
The complex Os(η1-MeC6H4L)(PPh3)2(CO)(η2-PhCO2) was
similarly prepared. Anal. Calcd for OsC59H49NO4P2: C, 65.09;
H, 4.54; N, 1.29. Found: C, 65.01; H, 4.53; N, 1.35.
mg (80%). Anal. Calcd for RuC52H44NO2P2Cl: C, 68.35; H,
4.85; N, 1.53. Found: C, 68.31; H, 4.80; N, 1.50. The complex
was characterized with the help of spectra and other features.1
X-r a y Str u ctu r e Deter m in a tion . A single crystal (0.28
× 0.12 × 0.36 mm3) of Ru(η1-MeC6H4L)(PPh3)2(CO)(η2-MeCO2)
grown (at 298 K) by slow diffusion of hexane into benzene
solution was used. The Ru(η1-MeC6H4L)(PPh3)2(CO)(η2-
PhCO2) compound was initially nonsolvated, but the single
crystals grown by slow diffusion of hexane into benzene
solution contain one molecule of benzene as a solvent of
crystallization. A single crystal of size 0.10 × 0.22 × 0.38 mm3
for this compound was used. Cell parameters were determined
by least-squares fit of 30 machine-centered reflections (rotation
photo) for both the cases. Data were collected by the ω-scan
technique in the range 2° e 2θ e 50° on a Siemens R3m/V
four-circle diffractometer with graphite-monochromated Mo
KR radiation (λ ) 0.710 73 Å). Two check reflections measured
after every 98 reflections showed no significant intensity
reduction in any cases. All data were corrected for Lorentz-
polarization effects, and an empirical absorption correction18
was done on the basis of an azimuthal scan of six reflections
for each crystal. Of the 9051 (Ru(η1-MeC6H4L)(PPh3)2(CO)-
(η2-MeCO2)) and 10 012 (Ru(η1-MeC6H4L)(PPh3)2(CO)(η2-
PhCO2)‚C6H6) reflections collected, 8571 and 9404 were re-
spectively unique of which 4531 and 2975 satisfying I > 3σ(I)
were respectively used for structure solutions and refinement.
There were no systematic absences, and the structures were
successfully solved in the space group P1h.
In each case the metal atom was located from Patterson
maps, and the rest of the non-hydrogen atoms emerged from
successive Fourier synthesis. The structures were refined by
full-matrix least-squares procedures. All the non-hydrogen
atoms of Ru(η1-MeC6H4L)(PPh3)2(CO)(η2-MeCO2) were refined
anisotropically, and the hydrogen atoms were located by
difference maps and refined with a fixed U ) 0.08 Å2 using a
riding model. All the non-hydrogen atoms except two PPh3
Con ver sion of Ru (η1-MeC6H4L)(P P h 3)2(CO)(η2-MeCO2)
to Ru (η2-MeC6H4L)(P P h 3)2(CO)Cl. To a stirred solution of
Ru(η1-MeC6H4L)(PPh3)2(CO)(η2-MeCO2) (10 mg) in acetone (5
mL)-dichloromethane (2 mL) mixture were added two drops
of 0.3 N HCl solution in acetone. The solution immediately
changed from yellow to violet. Stirring was continued for
another 10 min. The solvent was then removed under vacuo,
water was added to the violet residue, and the suspension was
stirred. This solid was collected by filtration. It was washed
repeatedly with water and dried in vacuo. The yield was 7.5
(18) North, A. C. T.; Phillips, D. C.; Mathews, F. A. Acta Crystallogr.,
Sect. A 1968, A24, 351.
Ghosh, Prasanta
