Method for preparation of a ruthenium indenylidene complex

Abstract

The present invention is directed to a method for the preparation of ruthenium catalyst (PCy.sub.3).sub.2Cl.sub.2Ru(phenylindenylidene) (Umicore catalyst M1). The method comprises a one-step reaction reacting the precursor compound (PPh.sub.3).sub.2Cl.sub.2Ru(3-phenylindenylidene) with PCy.sub.3 in a cyclic ether solvent (preferably THF) in concentrations in the range of 0.2 to 0.6 mol catalyst/l while simultaneously precipitating the product from the reaction mixture. A cyclic ether solvate product with high crystallinity and high purity is obtained.

Claims

1. A ruthenium-indenylidene carbene catalyst of Formula 1, ##STR00008## being present in a crystalline THF solvate form and showing peaks at diffraction angles (2) in XRD powder diffractometry (CuX-ray tube, tube excitation 40 kV, 40 mA) as listed in the following table: TABLE-US-00003 Peak No. diffraction angle (2) a about 7.3 b about 8.7 c about 9.8 d about 11.8 e about 14.2 f about 14.6 g about 17.3 h about 17.9 i about 18.8 j about 20.3.

2. The ruthenium-indenylidene carbene catalyst of claim 1, having a purity of >97%, as determined by .sup.31P-NMR spectroscopy.

3. The ruthenium-indenylidene carbene catalyst of claim 1, being present in a crystalline cyclic ether solvate form, comprising >1 molecule of cyclic ether per molecule of catalyst, as determined by .sup.1H-NMR and X-ray analysis.

4. The ruthenium-indenylidene carbene catalyst of claim 1, being present in a crystalline THF solvate form, comprising between 1 and 2 molecules of THF per molecule of catalyst, as determined by .sup.1H-NMR and X-ray analysis.

Description

EXAMPLES

(1) Generally, in the Examples glass reactors or flasks with condenser and stirrer are used for the method of the present invention. The reactors are flushed with dry inert gas (argon, nitrogen) prior to use.

(2) The NMR spectra are recorded on a BRUKER DRX 500 NMR spectrometer at about 25 C. The chemical shifts are determined relative to external phosphoric acid (.sup.31P-NMR) or to residual solvent signal (.sup.1H-NMR).

(3) The XRD diffractograms were recorded in the range 5<2<100 on a PANalytical X'Pert Pro with X-Celerator detector using Cu radiation. The sample material was prepared into a 27 mm PAN analytical sample holder (single preparation).

(4) The XRD data were recorded under the following conditions:

(5) TABLE-US-00002 Instrument PANalytical X'Pert Pro X-ray tube LFF-Cu-X-ray tube K-beta Filter Nickel Detector X'Celerator x-ray tube excitation 40 kV, 40 mA Divergence slit fixed Divergence slit size Anti-scatter slit 1 2-Theta range 5 to 100 Measurement Mode Continuous Time per step 40 s Step size 0.017 (2 Theta) Rotation 1 Rev/s

(6) The uncertainty in the peak position is +/0.05 2.

Example 1

Preparation of starting complex (PPh3)2Cl2O2Ru(3-phenylindenylidene) according to prior art (ref to H.-J. Schanz et al., cited above)

(7) A one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 800 ml of THF. The solvent is warmed up to 50 C. Then 19.7 g (98.6% purity, 93.2 mmol, 1.15 eq.) of 1,1-diphenyl-2-propyn-1-ol, 2.91 ml (40.5 mmol, 0.5 eq.; GFS Chemicals Inc., Powell, Ohio, USA) of acetylchloride and 99.6 g (81 mmol, 1 eq.) of Ru(PPh.sub.3).sub.3-4Cl.sub.2 (Ru-content 8.22 wt. %; Umicore AG & Co. KG, Hanau) are added successively during stirring. The reaction mixture is stirred under reflux (65 C.) for 90 min. Then it is cooled down to 50 C. and 700 ml of THF solvent are distilled off under vacuum. The red-brown suspension is cooled down to room temperature and isopropanol (600 ml) is added under stirring. The resulting precipitate is filtered off, washed with isopropanol and petroleum ether and then dried under vacuum at 40 C.

(8) Yield: 85% (based on Ru-content).

(9) .sup.31P-NMR (C.sub.6D.sub.6): =27.8 ppm (s)

Example 2

Preparation of dichloro(3-phenyl-1H-inden-1-ylidene)bis-(tricyclohexylphosphine)ruthenium(II) (according to the invention; c=0.5 mol/l)

(10) ##STR00007##

(11) A one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 500 ml of THF. The solvent is warmed up to 40 C. Then 221.7 g (250 mmol, 1 eq.) of (PPh.sub.3).sub.2Cl.sub.2Ru(3-phenylindenylidene) (Umicore AG & Co. KG, Hanau) and 155 g (98.1% purity, 540 mmol, 2.16 eq.) of tricyclohexylphosphine (PCy.sub.3, Aldrich) are added successively with stirring. The reaction mixture is stirred under reflux (65 C.) for 1 h during which time the product precipitates in form of dark red crystals. The reaction mixture is cooled down to 5 C. The crystalline precipitate is filtered off, washed with 400 ml of acetone and then dried under vacuum at 80 C. Yield: 236 g, 88% (based on Ru-content 9.41 wt.-%).

(12) .sup.31P-NMR (CD.sub.2Cl.sub.2): (ppm)=32.0 (s, product), 31.28 and 31.18 (side product). Purity based on .sup.31P-NMR: >99%.

(13) .sup.1H-NMR (CD.sub.2Cl.sub.2): (ppm)=8.66 (d, product, 1H), 7.96 (d, side product, <0.01H), 7.75 (m, product, 2H), 7.7 (m, side product, <0.02H), 7.52 (m, product, 1H), 7.40 (ms, product, 3H), 7.28 (m, product, 2H), 7.05 (td, side product, <0.01H), 7.016 (s, side product, <0.01H), 3.68 (m, THF, 6.4H), 2.60 (m, product, 6H), 1.9-1 (ms, product, 27H), 1.82 (m, THF, 6.4H). Other signals of the side product are covered by the signals of the product. THF-content based on .sup.1H-NMR=1.6 mol THF/mol product (11 wt.-%). Side-product content based on .sup.1H-NMR=<0.01 mol (<1 wt.-%).

(14) Bulk density: 0.45 g/ml

(15) Space yield: 236 g/l

Example 3

Preparation of dichloro(3-phenyl-1H-inden-1-ylidene)-bis-(tricyclohexylphosphine)ruthenium(II) (according to the invention; c=0.2 mol/l)

(16) A one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 600 ml of THF. Then 106.4 g (120 mmol, 1 eq.) of (PPh.sub.3).sub.2Cl.sub.2Ru(3-phenylindenylidene) (Umicore AG & Co. KG, Hanau) and 74 g (98.1% purity, 258 mmol, 2.15 eq.) of tricyclohexylphosphine, PCy.sub.3 are added successively with stirring. The reaction mixture is stirred under reflux (65 C.) for 0.5 hour. Then it is cooled down to 40 C. and 250 ml of THF solvent are distilled off causing the precipitation of the product in form of dark red crystals. Alternatively the solvent may be removed by a stream of inert gas during the reaction. The resulting red suspension is cooled down to 5 C. and acetone (500 ml) is added under stirring. The crystalline precipitate is filtered off, washed with acetone and then dried under vacuum at 80 C. Yield: 108 g, 85% (based on Ru-content, 9.54 wt.-%). Purity (.sup.31P-NMR): >99%. The analytical data of the product are comparable to those of Example 2.

(17) Space yield: 108 g/l

Comparative Example 4

Preparation of dichloro(3-phenyl-1H-inden-1-ylidene)-bis-(tricyclohexylphosphine)ruthenium(II) (according to EP 2280033, Example 9)

(18) A 500 ml Schlenk flask was purged with argon for 15 minutes. 5.21 mmol (5.0 g) RuCl.sub.2(PPh.sub.3).sub.3 and 8.49 mmol (1.79 g) 1,1-diphenyl-2-propin-1-ol were placed into the flask. 267 ml absolute tetrahydrofurane were added and the reaction mixture was stirred at reflux for 3 hours. The mixture was evaporated by 50% in vacuum and 16.67 mmol (4.76 g) tricyclohexylphosphine were added. The suspension was stirred for 8 hours at room temperature under argon. Then the solvent was removed in vacuum. The oily residue was added with 135 ml of acetone. The mixture was stored for 10 hours at 20 C. The residue was filtered by suction filtration (nutsche filter, porosity D4). The solid was washed with methanol, acetone and hexane. The product was dried in vacuum at room temperature. The product was obtained as brick-red powder, 4.63 g (5.02 mmol, 87% yield on metal base).

(19) Analysis

(20) Bulk density: 0.25 g/ml

(21) Space yield: about 14 g/L

(22) Purity (.sup.31P NMR): about 80%.

(23) THF-content (based on .sup.1H NMR, CD.sub.2Cl.sub.2, 20 C.): <0.1 mol THF/mol product (<0.5 wt.-%).

(24) .sup.31P and .sup.1H-NMR data shows the presence of several side products: diphenylallenylidene complex (41 ppm in .sup.31P NMR) and phosphine oxides.