5262 Organometallics, Vol. 29, No. 21, 2010
Miao et al.
cross-metathesis of an internal CdC bond diester with acrylo-
nitrile.
Preparation of RuCl(SnCl3)(dCHC6H4OPri)(H2IMes) (4).
To a solution of 100 mg (0.16 mmol) of the green complex 3
in 20 mL of THF was added an excess of dry SnCl2 (152 mg, 0.8
mmol). The solution was stirred for 72 h at 50 °C with moni-
toring by TLC (dark green spot, Rf = 0.25, 1/1 acetone/
hexane). The solvent was removed under vacuum; the solid
was extracted three times with 30 mL of CH2Cl2. The green
solution was concentrated to 25 mL, and then 15 mL of hexane
was added and the mixture was concentrated until the begin-
ning of crystallization. After a night at 0 °C the dark green
crystals that formed were filtered and dried under vacuum (92
mg, 70% yield). 1H NMR (300.13 MHz, CDCl3; δ, ppm): 1.34
Experimental Section
General Procedures. All reactions were performed under an
argon atmosphere using Schlenk techniques. Reagent grade
solvents were dried by the standard procedures and were freshly
distilled prior to use. Transmittance FT-IR spectra were recorded
using a Bruker IFS 28 spectrophotometer. 1H NMR and 31P{1H}
NMR were recorded on a Bruker AM 300WB spectrometer
operating at 300.13 and 121.5 MHz, respectively. 31P{1H} NMR
spectra were externally referenced against 85% ortho-H3PO4.
Elemental analyses were performed with the microanalysis instru-
ment Flash EA1112 CHN/O Thermo Electron at the CRMPO,
(d, 3 H, JHH = 6.1 Hz, CH3-iPr) ; 1.39 (d, 3 H, JHH = 6.1,
CH3-iPr); 2.31, 2.37, 2.45, 2.55, 2.66, 2.71 (6 s, 18 H, 6 CH3-
mesityl); 4.16-4.35 (m, 4 H, NCH2CH2N); 5.00-5.09 (m, 1 H,
OCH); 6.86-7.19 (m, 7 H, CH arom); 7.59-7.65 (m, 1 H, CH
arom); 15.65 (s þ 2 satellites, 1 H, 3J117Sn-1H= 3J119Sn-1H =
68.7 Hz, RudCH). IR spectrum (KBr, cm-1): C-H (2980 m,
2917 m, 1256 m, 1216 m, 854 m 595 vw, 510 w), Ph (1627 s, 1445
s, 1082 m, 1028 m, 730 w, 696 w). Anal. Calcd for C31H38Cl4-
3
3
ꢀ
Unversite de Rennes 1. The catalytic reactions were monitored
using a Shimadzu 2014 gas chromatograph equipped with
Equity-1 fused silica capillary column. RuCl2(dCHPh)(PCy3)2
(1) and RuCl2(dCHC6H4OPri)(H2IMes) (3) and anhydrous SnCl2
98% were purchased respectively from Sigma-Aldrich and Alfa-
Aesar. Fatty derivatives 5 and 7 were purchased from Acros,
compound 6 was offered by Arkema France, and the diester 13
was synthesized by esterification of the corresponding diacid offered
by Arkema France. All the cross-metathesis products are known int
he literature and their obtained spectroscopic data can be found in
the Supporting Information.
N2ORuSn 0.5CH2Cl2): C, 44.06; H, 4.58; N, 3.26. Found: C,
43.78; H, 4.64; N, 3.29.
3
General Procedure for Cross-Metathesis of Fatty Derivatives
with Acrylonitrile. In a Schlenk tube under argon, 0.5 mmol of
fatty derivatives and acrylonitrile (53 mg, 1 mmol) were dis-
solved in 10 mL of distilled toluene with dodecane as internal
standard; ruthenium catalyst (0.0025 mmol, 0.5 mol %) was
then added, and the reaction mixture was stirred at 80 °C for
various periods of time. A sample of the reaction mixture was
taken, filtered on a small pad of silica, and analyzed by GC. The
reaction product was purified by column chromatography on
silica gel.
X-ray Diffraction Analysis. Details of the data collection and
structure refinement for complexes 2 and 4 are presented in
Table S1 (Supporting Information). Single-crystal X-ray dif-
fraction experiments were carried out at T = 100 K on a Bruker-
ꢀ
AXS APEXII diffractometer (Centre de Diffractometrie X,
Sciences Chimiques de Rennes) and at T = 150 K on a Bruker
SMART APEXII diffractometer, for complexes 2 and 4, re-
spectively. Both diffractometers are equipped with a CCD area
detector and use Mo KR radiation (graphite monochromator, λ
= 0.710 73 A). The semiempirical method SADABS was ap-
plied for absorption correction. The structures were solved by
direct methods and refined by the full-matrix least-squares
technique against F2 with anisotropic displacement parameters
for all non-hydrogen atoms. All the hydrogen atoms in the
complexes were placed geometrically and included in the struc-
ture factor calculations in the riding motion approximation. All
of the data reduction and further calculations were performed
using the SAINT and SHELXTL program package.21 The
crystal structures have been deposited at the Cambridge Crystal-
lographic Data Centre and allocated the deposition numbers
CCDC 772944 (2) and 772694 (4).
General Procedure for Cross-Metathesis of Fatty Derivatives
with Methyl Acrylate. In a Schlenk tube under argon, 0.5 mmol
of fatty derivatives and methyl acrylate (86 mg, 1 mmol) were
dissolved in 1 mL of distilled toluene with dodecane as internal
standard, ruthenium catalyst (0.0025 mmol, 0.5 mol %) was
then added, and the reaction mixture was stirred at 50 °C or at
room temperature for various periods of time. A sample of the
reaction mixture was taken, filtered on a small pad of silica, and
analyzed by GC. The reaction product was purified by column
chromatography on silica gel.
General Procedure for Self-Metathesis of Undecylenic Alde-
hyde 5. In a Schlenk tube under argon, 84 mg (0.5 mmol) of
aldehyde 5 was dissolved in 2.5 mL of distilled toluene with
dodecane as internal standard. The ruthenium catalyst was then
added, and the reaction mixture was stirred at 40 °C for various
periods of time. The reaction was monitored using gas chroma-
tography.
Preparation of [Ru(dCHC6H5)(SnCl3)(PCy3)]2(μ-Cl)3]--
[HPCy3]þ (2). To a solution of 100 mg (0.12 mmol) of the purple
complex RuCl2(dCHPh)(PCy3)2 (1) in 20 mL of THF was added
an excess of SnCl2 (70 mg, 0.36 mmol). The solution was stirred for
4 h at room temperature with monitoring by TLC (yellow-green
spot, Rf=0.4, 1/1 CH2Cl2/hexane). The solvent was removed under
vacuum, the greenish yellow solid was extracted with 30 mL of
CH2Cl2, and the solution was filtered. A 15 mL portion of hexane
was added to the filtrate, the solution was concentrated until the
crystallization started, and then 3 mL of diethyl ether was added.
After a night at 0 °C the green crystals that formed were filtered and
dried under vacuum (80 mg, 75% yield). 1H NMR (300.13 MHz,
CDCl3; δ, ppm): 1.23-1.38 (m, 30H); 1.67-1.87 (m, 60H); 2.19 (s,
Acknowledgment. We are grateful to Arkema Co. for a
Ph.D. position to X.M., the PICS CNRS-Russian Foun-
dation of Basic Research (RFBR) (Nos. 07-03-92171 and
09-03-00961), the GDRE CNRS-Russia CH2D, the In-
stitut Universitaire de France for support to P.H.D., and
the Foundation of President of the Russian Federation
(program for support of leading Russian scientific
schools NSh-1733.2008.3).
1H); 2.35-2.42 (m, 3H), 7.55-7.75 (m, 10H); 8.67 (d, 2H, 3JHH
=
Supporting Information Available: CIF files giving full details
of the crystal structure analyses for complexes 2 and 4, tables
giving crystal data and structure refinement details, atomic
coordinates, bond lengths and angles, and hydrogen coordi-
nates, and text giving additional characterization data. This
material is available free of charge via the Internet at http://
pubs.acs.org. The data for X-ray diffraction analysis of com-
plexes 2 and 4 can also be obtained free of charge from The
ac.uk/data_request/cif.
7.3 Hz, dCH). 31P{1H} NMR (121.5 MHz, CDCl3;δ, ppm): 23.837
(s), 48.134 (s). IRspectrum (KBr, cm-1):C-H (2929 s, 2852 s, 1297
m, 1259 m, 1205 m 1176 m, 1121 m, 567 w, 517 m), Ph (1446 s, 1077
s, 1005 m, 924 m, 875 m, 850 m, 727 m, 699 m). Anal. Calcd for
C68H112Cl9P3Ru2Sn2 2(C2H5)2O: C, 47.31; H, 6.90. Found: C,
47.65; H, 6.37.
3
(21) Sheldrick, G. M. SHELXTL-97, Version 5.50; Bruker AXS Inc.,
Madison, WI 53719. 1997.