Y.-B. Lai et al. / Polyhedron 53 (2013) 243–248
247
measured on a Micromass Platform II spectrometer. Elemental
4.5. X-ray data collection and structure refinement
microanalyses were performed at the Taiwan Instrumentation Cen-
ter. GC analyses were performed with a GC9800 gas chromatogra-
phy instrument (Shanghai Kechuang Chromatograph Instrument
Co.) equipped with a flame ionization detector and a 10 m
Single
crystals
(CH CN)
of
](BF
[Ru(MeCCmeth
) suitable for X-ray diffraction were
4 2
)
2
(CH
3
CN)
2
](BF
4
)
2
and
[Ru( CCmeth
Bu
)
2
3
2
mounted on the tips of glass fibers with epoxy resin and the X-
ray diffraction intensity data were collected on a Bruker APEX II
(
2.65
lm film thickness) RESTEK Rtx-2887 fused silica capillary
column.
CCD XRD. All data were collected with
x scan technique using
graphite monochromatic Mo K radiation (k = 0.71073 Å). Data
a
4
4
.2. Preparation of the complexes
reduction was performed with SAINT, which corrects for the Lorentz
and polarization effects. Absorption corrections were performed
using multiscan (SADABS) [18]. All non-hydrogen atoms were refined
with anisotropic displacement parameters and hydrogen atoms
were refined using a ‘maXus’ model. The structures were solved
by the use of direct methods using SHELXL-97 program and refined
Me
meth
.2.1. [Ru( CC
RuCl (COD)]
trile solution (15 mL) containing [Ag
mmol) and the mixture was refluxed for 24 h, followed by filtra-
)
2
(CH
3 2 4 2
CN) ](BF )
[
2
n
(0.7766 g, 2 mmol) was added into the acetoni-
Me
meth
2
(
CC
2 4 2
) ](BF ) (1.483 g,
2
2
tion to yield a clear pale yellow filtrate. The filtrate was concen-
by full-matrix least-squares methods on F using SHELXL-97 [19].
trated to ca. 5 mL in vacuo and further addition of ether yielded a
Complete structure data have been deposited. Salient crystal data
white precipitate. Yield: 65%. 1H NMR (DMSO-d
): d 7.61 (d, 4H,
imi-H), 7.35 (d, 4H, imi-H), 6.33 (d, JH–H = 13.1 Hz, 2H, NCH N),
), 2.22 (s,
): d 188.5 (NCN carbenoid C),
CN), 122.7, 122.6 (imi-C), 62.7 (NCH N), 36.1 (NCH ),
CN). Mass (MALDI): m/z = 607 (M + BF ) , 495
are: C24
6
33 2 8 f 1
H B F N11Ru, M = 750.30, monoclinic, space group P2 /c,
2
T = 100(2) K, a = 13.7590(10) Å, b = 12.0721(9) Å, c = 20.0888(15)
3
3
6
6
1
4
.22 (d, JH–H = 13.1 Hz, 4H, NCH
2
N), 3.41 (s, 12H, NCH
CN). C NMR (DMSO-d
27.1 (CH
.1 (CH
3
Å, b = 101.8750(10)°, V = 3265.3(4) Å , Z = 4, Dcalc = 1.526 g/cm ,
l
1
3
ꢀ1
H, CH
3
6
= 0.561 mm , hrange = 1.51–28.41°. Of 23857 reflections col-
3
2
3
lected, 8173 were independent, Rint = 0.0281, and 7009 were
observed (I > 2 (I)); final indices: Goodness-of-fit = 1.090,
= 0.0399 (I > 2 (I)), wR = 0.1113.
10Ru, M = 877.56, monoclinic, space group P2
T = 395(2) K, a = 10.358(2) Å, b = 19.421(4) Å, c = 11.682(2) Å,
+
3
4
ꢀCH
3
r
R
+
+
Me
meth +
Me-
(
MꢀCH
3
CN) , 454 (Mꢀ2CH
3
CN) , 359 (Mꢀ CC
) , and 177 (
R
1
r
2
meth
+
CC
+ H) . Anal. Calc. for C22 10Ru: C, 37.26; N, 19.75; H,
H
30
2
B F
8
N
C
34
H B
54 2
F
8
N
f
1
,
4
.26. Found: C, 37.14; N, 19.70; H, 4.39%.
3
3
b = 116.31°,
V = 2107.2(8) Å ,
Z = 2,
range = 1.94–26.43°. Of 13770 reflections
collected, 6970 were independent, Rint = 0.0630 and 5028 were
observed (I > 2 (I)); final indices: Goodness-of-fit = 0.938,
= 0.0562 (I > 2 (I)), wR = 0.1249.
Dcalc = 1.383 g/cm ,
Bu
meth
ꢀ1
4
.2.2. [Ru( CC
[
)
2
(CH
(CH CN)
the same procedure as that of [Ru( CC
3
CN)
2
](BF
4
)
2
l
= 0.445 mm
,
h
Ru( CCmeth)
Bu
](BF
2
3
2
4 2
) was synthesized by following
Me
meth
)
2
(CH
): d 7.69 (d, 4H, imi-H), 7.44 (d,
H, imi-H), 6.61 (d, JH–H = 13.5 Hz, 2H, NCH N), 6.47 (d, JH–
= 13.5 Hz, 2H, NCH N), 3.92 (t, JH–H = 7.5 Hz, 8H, NCH CH CH2-
), 2.39 (s, 6H, CH CN), 1.83 (m, 8H, NCH CH CH CH ), 1.29
m, 8H, NCH CH CH CH ), 0.83 (t, JH–H = 7.5 Hz, 12H, NCH CH
). C NMR (DMSO-d ): d 187.6 (NCN carbenoid C), 126.6 (CH3-
N), 48.7 (NCH CH CH CH ),
CH CH CH ), 13.7 (NCH
CN) ppm. Mass (MALDI): m/z = 836 (M + 2BF4-
3
CN)
2
](BF
4
)
2
.
r
R
1
Yield: 83%. H NMR (DMSO-d
6
R
1
r
2
4
2
H
2
2
2
Acknowledgments
CH
(
CH
3
3
2
2
2
3
2
2
2
3
2
2
CH2-
Financial support from the National Science Council (Taiwan,
ROC) and National Dong Hwa University are gratefully
acknowledged.
1
3
3
6
CN), 123.1, 120.7 (imi-C), 62.7 (NCH
2.7 (NCH CH CH CH ), 20.2 (NCH
CH CH ), 4.4 (CH
CH CN) ,
2
2
2
2
3
3
2
2
2
3
2
2
2
3
2
CH2-
2
3
3
Appendix A. Supplementary material
+
+
ꢀ
3
795
10Ru: C, 46.54; N, 15.96; H, 6.20. Found: C, 46.40; N,
5.48; H, 5.86%.
(M + 2BF
4
ꢀ2CH
3
CN) .
Anal.
Calc.
for
C
34 54 2 8
H B F N
CCDC 823968 and 823969 contain the supplementary crystallo-
1
Me
meth
Bu-
graphic data for [Ru( CC
CC
)2(CH3CN)2](BF4)2 and [Ru(
meth
4.3. General procedure for the transfer hydrogenation of ketones
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
In
a
standard experiment, the ruthenium(II) complex
i
(
1.0 mol%), NaOH (0.20 mmol), and 2 mL of PrOH was charged into
a screw capped vial under aerobic conditions, followed by heating
at 82 °C. After 20 min of heating, the organic substrate (1.0 mmol)
was added into this reaction mixture and further heating was con-
tinued at 82 °C. The reaction was monitored by GC analysis.
References
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(
(
b) E. Peris, R.H. Crabtree, Coord. Chem. Rev. 248 (2004) 2239;
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(
(
(
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[
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Me
meth
[
[
reaction was carried out with 0.1 mol% [Ru( CC
BF )
4 2
)
2
(CH
and 0.2 mmol of NaOH in 2 mL of 2-propanol at 100 °C for
0 min, followed by the addition of 1 mmol cyclohexanone. After
3 2
CN) ]
(
2
(
b) J.A. Mata, M. Poyatos, E. Peris, Coord. Chem. Rev. 25 (2007) 841;
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(
5] (a) G. Su, X.K. Huo, G.X. Jin, J. Organomet. Chem. 696 (2011) 533;
(
(2011) 195;
(
(
the completion of the reaction, the reaction mixture was cooled
and the mixture was extracted with diethyl ether or dichlorometh-
e) O. Kühl, Chem. Soc. Rev. 36 (2007) 592.
[
[
ane/H
2
O (3 mL/2 mL) four times. The organic phase was separated
_
b) S. Demir, I. Özdemir, B. Çetinkaya, H. Arslan, D.V. Derveer, Polyhedron 30
and the aqueous layer was decanted. The residue was dried in va-
cuo before next cycle. The same amount of cyclohexanone, 2-pro-
panol, and NaOH were added as in the original reaction, and the
reaction was continued for the next run.
c) M. Poyato, J.A. Mata, E. Peris, Chem. Rev. 109 (2009) 3677;
d) M. Poyatos, E. Mas-Marzá, M. Sanaú, E. Peris, Inorg. Chem. 43 (2004) 1793.
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297;