Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis

• US 20040095792A1
• Filed: 07/29/2003
• Published: 05/20/2004
• Est. Priority Date: 04/06/1998
• Status: Active Grant

• Current Assignee: Thomas Weskamp, Wolfgang Anton Herrmann, Wolfgang Schattenmann
• Original Assignee: Evonik Degussa GmbH
• Inventors: Schattenmann, Wolfgang, Herrmann, Wolfgang Anton, Weskamp, Thomas
• Granted Patent: US 7,294,717 B2
• Time in Patent Office: Days
• US Class Current: 365/21
• CPC Class Codes: B01J 2231/14 Other (co) polymerisation, e.g. of lactides, epoxides "ROMP", i.e. ring-opening metathesis polymerisation B01J2231/54
• CPC Class Codes: B01J 2231/54 Metathesis reactions, e.g. olefin metathesis
• CPC Class Codes: B01J 2231/543 alkene metathesis
• CPC Class Codes: B01J 2531/0263 Planar chiral ligands, e.g. derived from donor-substituted paracyclophanes and metallocenes or from substituted arenes
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 31/18 containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265
• CPC Class Codes: B01J 31/2208 Oxygen, e.g. acetylacetonates
• CPC Class Codes: B01J 31/2265 Carbenes or carbynes, i.e.(image)
• CPC Class Codes: B01J 31/2273 with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
• CPC Class Codes: B01J 31/2404 Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
• CPC Class Codes: B01J 31/26 containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 13/20 with a cyclohexene ring
• CPC Class Codes: C07C 2/32 as complexes, e.g. acetyl-acetonates complexes of salts of acids of halogen C07C2/20
• CPC Class Codes: C07C 2531/22 Organic complexes
• CPC Class Codes: C07C 2531/24 Phosphines
• CPC Class Codes: C07C 6/04 at a carbon-to-carbon double bond
• CPC Class Codes: C07C 67/313 by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
• CPC Class Codes: C07C 67/475 by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07F 15/0046 : Ruthenium compounds
• CPC Class Codes: C08G 61/08 : of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Abstract

The invention relates to a complex of ruthenium of the structural formula I,

where X¹ and X² are identical or different and are each an anionic ligand,

R¹ and R² are identical or different and can also contain a ring, and R¹ and R² are each hydrogen or/and a hydrocarbon group,

the ligand L¹ is an N-heterocyclic carbene and the ligand L² is an uncharged electron donor, in particular an N-heterocyclic carbene or an amine, imine, phosphine, phosphite, stibine, arsine, carbonyl compound, carboxyl compound, nitrile, alcohol, ether, thiol or thioether,

where R¹, R², R³ and R⁴ are hydrogen or/and hydrocarbon groups.

The invention further relates to a process for preparing acyclic olefins having two or more carbon atoms or/and cyclic olefins having four or more carbon atoms from acyclic olefins having two or more carbon atoms or/and from cyclic olefins having four or more carbon atoms by an olefin metathesis reaction in the presence of at least one catalyst, wherein a complex is used as catalyst and R′¹, R′², R′³ and R′⁴ are hydrogen or/and hydrocarbon groups.

Claims

1. A complex of ruthenium of the structural formula I,

2. A complex as claimed in claim 1, wherein the identical or different anionic ligands X¹ and X² are each halide, pseudohalide, tetraphenylborate, perhalogenated tetraphenylborate, tetrahaloborate, hexahalophosphate, hexahaloantimonate, trihalomethanesulfonate, alkoxide, carboxylate, tetrahaloaluminate, tetracarbonylcobaltate, hexahaloferrate(III), tetrahaloferrate(III) or/and tetrahalopalladate(II),

with preference being given to halide, pseudohalide, tetraphenylborate, perfluorinated tetraphenylborate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate, alkoxide, carboxylate, tetrachloroaluminate, tetracarbonylcobaltate, hexafluoroferrate (III), tetrachloroferrate(III) or\and tetrachloropalladate(II) and preferred pseudohalides being cyanide, thiocyanate, cyanate, isocyanate and isothiocyanate.

3. A complex as claimed in claim 1 or 2, wherein some or all of the hydrogen atoms in the hydrocarbon groups R¹, R², R³ and R⁴ in the formulae II, III, IV and V are replaced independently by identical or different halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, sulfonyl or/and metallocenyl groups.

4. A complex as claimed in any one of claims 1 to 3, wherein R³ and R⁴ in the formulae II, III, IV and V form a fused-on ring system.

5. A complex as claimed in any one of claims 1 to 4, where in L¹ and L² form a chelating ligand of the formula VI

L¹-Y-L² 

 

VI

where the bridges Y can comprise cyclic, noncyclic, straight-chain or/and branched radicals selected from the group consisting of alkylene radicals having from 1 to 50 carbon atoms, alkenylene radicals having from 1 to 50 carbon atoms, alkynylene radicals having from 1 to 50 carbon atoms, arylene radicals having from 1 to 30 carbon atoms, metallocenylene, borylene and silylene radicals in which one or more hydrogens may be replaced independently by identical or different alkyl, aryl, alkenyl, alkynyl, metallocenyl, halo, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or/and sulfonyl groups, preferably alkyl, aryl or/and metallocenyl groups.

6. A complex as claimed in any one of claims 1 to 5, wherein the ligands of the formulae II, III, IV, V or/and VI have central, axial or/and planar chirality.

7. A complex as claimed in any one of claims 1 to 6, wherein R¹ and R² in the structural formula I are hydrogen, substituted or/and unsubstituted alkyl, alkenyl or/and aryl radicals, X¹ and X² are halide, alkoxide or/and carboxylate ions or/and L¹ and L² are each an N-heterocyclic carbene of the formula II.

8. A process for preparing acyclic olefins having two or more carbon atoms or/and cyclic olefins having four or more carbon atoms, in each case of the formula VII

9. The process as claimed in claim 8, wherein one or more double bonds are present in the olefins used.

10. The process as claimed in claim 8 or 9, wherein R′

¹, R′

², R′

³ and R′

⁴ in the olefins of the formula VII to be prepared form, in pairs, one or more identical or different rings.

11. The process as claimed in any one of claims 8 to 10, wherein some or all of the hydrogen atoms in the hydrocarbon groups R′

¹, R′

², R′

³ and R′

⁴ of the olefins of the formula VII to be prepared are replaced independently by identical or different halogen, silyl, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, sulfonyl or/and metallocenyl groups.

12. The process as claimed in any one of claims 8 to 11, wherein the process is carried out in the presence or absence of solvents, but preferably in the presence of organic solvents.

13. The process as claimed in any one of claims 8 to 12, wherein the process is carried out with addition of a Bronsted acid, preferably HCl, HBr, HI, HBF₄, HPF₆ or/and trifluoroacetic acid.

14. The process as claimed in any one of claims 8 to 12, wherein the process is carried out with addition of a Lewis acid, preferably BF₃, AlCl₃ or/and ZnI₂.