Ruthenium complexes, method of their production and their usage

Abstract

The invention concerns the ruthenium complexes of the formula 1: ##STR00001##
acting as pre(catalysts) in the reaction of metathesis of olefins, as well as a method for their production, and their usage.

Claims

1. A ruthenium complex of formula 1: ##STR00035## wherein: L is a neutral ligand; X.sup.1 and X.sup.2 independently represent an anionic ligand; R.sup.1, R.sup.2, R.sup.a, R.sup.b, R.sup.c, R.sup.d independently represent a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.3-C.sub.7 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.20 heteroaryl, 3-12-membered heterocyclyl, ether (OR), thioether (SR), nitro (NO.sub.2), cyano (CN), carboxy and ester (COOR), amido (CONRR), sulphono (SO.sub.2R), sulphonamido (SO.sub.2NRR), formyl or keto (COR), wherein R and R independently represent a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.24 heteroaryl, or C.sub.5-C.sub.24 perfluoroaryl; Z independently represents formyl and keto (COR.sup.Z), carboxy and ester (COOR.sup.Z), thioester (CSOR.sup.Z), or amido (CONR.sup.ZR.sup.Z), wherein R.sup.Z and R.sup.Z independently represent a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.24 heteroaryl, or C.sub.5-C.sub.24 perfluoroaryl; the anionic ligands X.sup.1, X.sup.2 independently represent a halogen atom, CN, SCN, OR.sup.4, SR.sup.4, O(CO)R.sup.4, O(SO.sub.2)R.sup.4, OP(O)R.sub.2.sup.4, or OSiR.sub.3.sup.4, where R.sup.4 is C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, or C.sub.5-C.sub.20 aryl, being optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhaloalkyl, C.sub.1-C.sub.12 alkoxy or a halogen atom; and the neutral ligand L is a N-heterocyclic carbene ligand selected independently from the group consisting of formula 2a, 2b, 2f, and 2g: ##STR00036## wherein: each R.sup.50, and R.sup.60 independently represents C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.5-C.sub.20 aryl, or C.sub.5-C.sub.20 heteroaryl, being optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhaloalkyl, C.sub.1-C.sub.12 alkoxy or a halogen atom; each R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 independently represents a hydrogen atom, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.5-C.sub.20 aryl, or C.sub.5-C.sub.20 heteroaryl, being optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perhaloalkyl, C.sub.1-C.sub.12 alkoxy or a halogen atom; and wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.50, and R.sup.60, may optionally bind each other to form a cyclic or macrocyclic system.

2. The complex according to claim 1, wherein the ligands X.sup.1 and X.sup.2 denote a chlorine atom.

3. The complex according to claim 1, wherein the neutral ligand L denotes a ligand of formula 2a or 2b: ##STR00037## wherein the substituents R.sup.50, R.sup.60, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are as above defined.

4. A ruthenium complex being represented by formula 1a: ##STR00038##

5. A process for preparation of the ruthenium complex as defined in claim 1, comprising: reacting a compound of formula 3 ##STR00039## wherein: R, R.sup.1, R.sup.2, R.sup.a, R.sup.b, R.sup.c, R.sup.d and Z are as above defined, and R.sup.13, R.sup.14 independently represent a hydrogen atom, a halogen atom, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.3-C.sub.7 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.20 heteroaryl, 3-12-membered heterocyclyl, preferably, a hydrogen atom, nitro (NO.sub.2), cyano (CN), carboxy or ester (COOR.sup.X), amido (CONR.sup.XR.sup.X), sulphono (SO.sub.2R.sup.X), sulphonamido (SO.sub.2NR.sup.XR.sup.X), formyl or keto (COR.sup.X), wherein R.sup.X and R.sup.X independently represent a hydrogen atom, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, or C.sub.5-C.sub.24 aryl; with a carbene ruthenium complex of formula 4a, 4b, 4c or 4d: ##STR00040## wherein: L.sup.1, L.sup.2 and L.sup.3 independently represent a neutral ligand; X.sup.1 and X.sup.2 independently represent an anionic ligand; R.sup.11 is identical to R.sup.1 in formula 1; R.sup.12 is a hydrogen atom, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 heteroaryl, vinyl or allenyl, wherein, the reaction is carried out in a period of from 1 min to 250 hrs, at a temperature of from 0 to 150 C., in a protic solvent or in an aprotic, chlorinated solvent or in an aromatic hydrocarbon solvent or in a mixture thereof, in the presence of oxygen.

6. The process according to claim 5, wherein the reaction is carried out in a solvent selected from the group comprising methylene chloride, toluene or a mixture thereof.

7. A process of using the ruthenium complex as claimed in claim 1 as a catalyst in the metathesis of olefins, comprising contacting the complex of formula (I) with an olefin.

8. The process according to claim 7, wherein the catalysed metathesis of olefins comprises a reaction selected from ring-closing metathesis, homometathesis, cross-metathesis, alkene-alkyne type metathesis or ring-opening metathetic polymerisation.

9. The process according to claim 8, wherein the catalysed metathesis is the ring-opening metathetic polymerisation of dicyclopentadiene.

10. The process of claim 7 wherein the catalysed reaction of metathesis of olefins is reversibly retarded by addition of an acid or halogen derivatives of alkanes and silanes.

Description

BRIEF DESCRIPTION OF FIGURES OF DRAWINGS

(1) For better understanding, the invention has been illustrated in examples of embodiment as well as in enclosed figures of drawings, of which:

(2) FIG. 1 presents Diagram 1Kinetic profiles of the reaction progress with a catalyst of the formula 1a at the temperatures of 40, 80 and 120 C. according to Scheme IX

(3) FIG. 2 presents Diagram 2Kinetic profiles of the reaction progress with a catalyst of the formula 1a in toluene at a temperature of 80 C. according to Scheme IX.

(4) FIG. 3 presents Diagram 3Kinetic profiles of the reaction progress with a catalyst of the formula 1a in mesitylene at a temperature of 120 C. according to Scheme IX.

METHODS OF PUTTING THE INVENTION INTO PRACTICE

(5) The following examples explain preparation and use of novel ruthenium complexes according to the invention.

EXAMPLES

Example I

Synthesis of the Catalyst of the Formula 1a

(6) ##STR00030##

(7) Procedure A (according to Scheme I): Using the protective argon atmosphere, the Schlenk vessel was charged with anhydrous CuCl (0.0198 g, 0.2 mmol, 2 equivalents), the compound of the formula 3:

(8) ##STR00031##

(9) (0.0246 g, 0.12 mmol, 1.2 equivalent), dry, deoxygenated toluene (4 ml) as well as a solid carbene complex of the metal of the formula 4c, wherein X.sup.1 and X.sup.2 denote chlorine, L.sup.1 denotes tricyclohexylphosphine (PCy.sub.3), L.sup.2 denotes an NHC ligand of the formula 2a, wherein R.sup.50 and R.sup.60 denote 2,4,6-trimethylphenyl, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 denote a hydrogen atom; and R.sup.12 denotes phenyl (complex Ind-II, 0.0949 g, 0.1 mmol). The obtained suspension was stirred at a temperature of 60 C. for 30 min. The protective argon atmosphere was replaced with air and warming at a temperature of 60 C. was continued for 30 min. The reaction mixture was chromatographed over silica gel, using 40% ethyl acetate in cyclohexane as an eluent. Then the product-containing fractions were combined, the solvents were distilled of on a rotary evaporator, leaving the catalyst of the formula 1a as a red solid (0.042 g, 64%).

(10) Procedure B (according to Scheme II): Using the protective argon atmosphere, the Schlenk vessel was charged with the styrene derivative 3 (0.0246 g, 0.12 mmol, 1.2 equivalent), dry, deoxygenated toluene (4 ml) as well as the solid carbene complex of the metal of the formula 4d, wherein X.sup.1 and X.sup.2 denote chlorine, L.sup.1 denotes pyridine, L.sup.2 denotes an NHC ligand of the formula 2a, wherein R.sup.50 and R.sup.60 denote 2,4,6-trimethylphenyl, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 denote a hydrogen atom; and R.sup.12 denotes phenyl (complex Ind-III, 0.0784 g, 0.1 mmol). The obtained suspension was stirred at a temperature of 80 C. for 15 min. The protective argon atmosphere was replaced with air and warming at a temperature of 80 C. for 20 min. The reaction mixture was chromatographed over silica gel, using 40% ethyl acetate in cyclohexane as an eluent. Then the product-containing fractions were combined, the solvents were distilled of on a rotary evaporator, to yield the catalyst of the formula 1a as a red solid (0.026 g, 40%).

(11) .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2): 16.95 (s, 1H, RuCHAr), 8.98 (s, 1H, NCHCOOMe), 7.57-7.54 (m, 1H), 7.40 (d, J=8 Hz, 1H), 7.32-7.29 (m, 1H), 7.05 (bs, 4H, CH.sub.2CH.sub.2), 6.98-6.96 (m, 1H), 4.07 (s, 4H), 3.62 (s, 3H, CH.sub.3O), 2.50 (bs, 12H), 2.39 (bs, 6H).

(12) .sup.13C NMR (125 MHz, CD.sub.2Cl.sub.2): 304.5 (RuCH), 208.7 (RuCNN), 169.3, 159.1, 141.9, 139.7, 138.7, 134.8, 129.5, 127.9, 121.5, 117.2, 54.4, 52.2, 21.2, 19.2.

(13) HR MS (ESI) Calculated for: C.sub.31H.sub.35N.sub.3O.sub.2NaCl.sub.2Ru ([M+Na].sup.+) m/z: 676.1048.

(14) Found: 676.1057.

(15) X-Ray structural analysis for the compound 1a:

(16) ##STR00032##
The examples of uses of the compound 1a as a catalyst in the ring-closure metathesis reaction as well as in the ROMP polymerisation are shown below.

Example II

Studies on Catalytic Activity in Cyclisation of Diethyl Diallylmalonate

(17) ##STR00033##

(18) Procedure A: The Schlenk vessel was charged with a solution of the diene S1 (96.1 mg, 0.4 mmol) in DCM (4 ml), followed by the catalyst 1a (2.61 mg, 1 mol %). The content of the vessel was stirred at a temperature of 40 C. under argon atmosphere. The crude reaction mixture was analysed using a gas chromatograph.

(19) Procedure B: The Schlenk vessel was charged with a solution of the diene S1 (96.1 mg, 0.4 mmol) in toluene (4 ml), followed by the catalyst 1a (2.61 mg, 1 mol %). The content of the vessel was stirred at a temperature of 80 C. under argon atmosphere. The crude reaction mixture was analysed using a gas chromatograph.

(20) Procedure C: The Schlenk vessel was charged with a solution of the diene S1 (96.1 mg, 0.4 mmol) in toluene (4 ml), to which was added a solution of HCl in dioxane (50 L, 50 mol %), followed by the catalyst 1a (2.61 mg, 1 mol %). The content of the vessel was stirred at a temperature of 80 C. under argon atmosphere. The crude reaction mixture was analysed using a gas chromatograph.

(21) Procedure D: The Schlenk vessel was charged with a solution of the diene S1 (96.1 mg, 0.4 mmol) in toluene (4 ml), to which was added chlorotrimethylsilane (3.46 L, 10 mol %), followed by the catalyst 1a (2.61 mg, 1 mol %). The content of the vessel was stirred at a temperature of 80 C. under argon atmosphere. The crude reaction mixture was analysed using a gas chromatograph.

(22) Procedure E: The Schlenk vessel was charged with a solution of the diene S1 (96.1 mg, 0.4 mmol) in mesitylene (4 ml), followed by the catalyst 1a (2.61 mg, 1 mol %). The content of the vessel was stirred at a temperature of 120 C. under argon atmosphere. The crude reaction mixture was analysed using a gas chromatograph.

(23) Procedure F: The Schlenk vessel was charged with a solution of the diene S1 (96.1 mg, 0.4 mmol) in mesitylene (4 ml), to which was added a solution of HCl in dioxane (50 L, 50 mol %), followed by the catalyst 1a (2.61 mg, 1 mol %). The content of the vessel was stirred at a temperature of 120 C. under argon atmosphere. The crude reaction mixture was analysed using a gas chromatograph.

(24) Procedure G: The Schlenk vessel was charged with a solution of the diene S1 (96.1 mg, 0.4 mmol) in mesitylene (4 ml), to which was added chlorotrimethylsilane (3.46 L, 10 mol %), followed by the catalyst 1a (2.61 mg, 1 mol %). The content of the vessel was stirred at a temperature of 120 C. under argon atmosphere. The crude reaction mixture was analysed using a gas chromatograph.

(25) The results are shown in diagrams 1-3 presented in FIGS. 1-3, respectively: Diagram 1 (FIG. 1), Diagram 2 (FIG. 2), Diagram 3 (FIG. 3).

(26) The presented results demonstrate that the complexes according to the invention are characterised by a good catalytic activity in the reaction of metathesis of olefins, and they are stable at elevated temperatures.

(27) Additionally, it was shown that addition of HCl or TMSCl resulted in a significant drop of catalytic activity of the complexes according to the invention. Removal of HCl or TMSCl from the reaction medium by heating resulted in recovering the initial catalytic activity of the complexes according to the invention.

Example III

Studies on Catalytic Activity in Polymerisation of Dicyclopentadiene

(28) ##STR00034##

(29) Procedure A: Under oxygen-containing atmosphere, the polymerisation vial was charged with dicyclopentadiene S2 (1 ml, 7.46 mmol), which after melting was stirred at a temperature of 30 C. Then the catalyst 1a (4.88 mg, 0.1 mol %) in DCM (0.1 ml) was added, and the open vial was heated under oxygen-containing atmosphere at a temperature of 60 C. for 15 min. A hard polymer was obtained.

(30) Procedure B: Under oxygen-containing atmosphere, the polymerisation vial was charged with dicyclopentadiene S2 (1 ml, 7.46 mmol), which after melting was stirred at a temperature of 30 C. Then the catalyst 1a (0.488 mg, 0.01 mol %) in DCM (0.1 ml) was added, and the open vial was heated under oxygen-containing atmosphere at a temperature of 60 C. for 15 min. A hard polymer was obtained.

(31) Procedure C: Under oxygen-containing atmosphere, the polymerisation vial was charged with dicyclopentadiene S2 (1 ml, 7.46 mmol), which after melting was stirred at a temperature of 30 C. Then chlorotrimethylsilane (0.65 l, 0.1 mol %) and the catalyst 1a (0.488 mg, 0.01 mol %) solution in DCM (0.1 ml) was added, and the vial content was left at a room temperature for 4 days. After this time, no polymer formation was observed. Then the solution was heated at a temperature of 150 C. in the open vial under oxygen-containing atmosphere for 15 min. A hard polymer was obtained.

(32) The above-presented examples of polymerisation reactions indicated that the compounds according to the invention are characterised by a good catalytic activity in the polymerisation reaction. Additionally, it is shown that the polymerisation process may be reversibly retarded by using chlorotrimethylsilane. This process is not known in the literature.