# US 7,612,008 B2 · Metathesis catalysts

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- Number: US 7,612,008 B2
- Document ID: US7612008B2
- Status: Granted
- Kind: B2
- Application number: 10/628,707
- Filed: 2003-07-28
- Published: 2004-05-06
- Granted: 2009-11-03
- Earliest claimed: 2002-07-31
- Assignees: LANXESS Deutschland GmbH
- Inventors: Siegfried Blechert; Stephen Connon
- Web page: https://patentgrep.com/patent/US7612008B2

## CPC

- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- B01J 31/1658: {immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins}
- B01J 31/2273: {with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes}
- C08G 61/122: {derived from five- or six-membered heterocyclic compounds, other than imides}
- C08G 61/125: {with a five-membered ring containing one oxygen atom in the ring}
- B01J 2231/543: alkene metathesis
- B01J 2531/821: Ruthenium
- B01J 2531/825: Osmium
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

The invention relates to polymeric transition metal catalysts, to processes for preparing them, to intermediates and also to the use of the transition metal catalysts as catalysts in organic reactions, in particular in olefin metathesis reactions.

## Claims

### Claim 1

A polymeric transition metal catalyst comprising:
a polymeric compound having a degree of polymerization numerical average value from 6 to 2000 and containing at least one transition metal catalyst comprising:
at least one structural unit of the formula (Ia):
where;
M is a transition metal of the 8th transition group of the Periodic Table;
X1 and X2 are the same or different and are each chlorine, bromine or iodine;
L is an N-heterocyclic carbene ligand of the formula (II):
where the direction of the arrow is intended to represent the bond to M and where;
B is a 1,2-ethanediyl or 1,2-ethenediyl radical which is optionally mono- or disubstituted by C1-C4-alkyl, C6-C15-arylalkyl or C5-C14-aryl; and
R6 and R7 are each independently C1-C20-alkyl or C5-C24-aryl;
R1 is cyclic, straight-chain or branched C1-C20-alkyl or C5-C24-aryl; and
R2, R3 and R4 are each independently hydrogen, C1-C20-alkyl, C5-C24-aryl, halogen, C1-C4-fluoroalkyl, C1-C4-alkoxy, C5-C14-aryloxy, (C1-C8-alkyl)OCO—, (C1-C8-alkyl)CO2—, (C5-C14-aryl)OCO— or (C5-C14-aryl)CO2—; and/or
in each case two radicals in an ortho-arrangement to one another from the group of R2, R3 and R4 are part of a cyclic system which consists of a carbon framework having 5 to 22 carbon atoms, one or more carbon atoms of the cyclic system optionally being replaced by heteroatoms from the group of sulphur, oxygen or nitrogen, and the cyclic system also being optionally mono- or polysubstituted by radicals selected from the group of halogen, C1-C4-fluoroalkyl, (C1-C4-alkyl)OCO—, (C1-C8-alkyl)CO2—, (C6-C10-aryl)OCO— or (C5-C14-aryl)CO2—; and
A is oxygen, sulphur, sulphoxyl, sulphonyl or CR8R9 where R8 and R9 are each independently hydrogen or C1-C4-alkyl; and
D is C1-C8-alkylene, [(C1-C8-alkylene)-O—]n where n=1 to 12, (C1-C8-alkylene)CO2—, (C1-C8-alkylene)-OCO—(C1-C8-alkylene), (C1-C8-alkylene)CO2—(C1-C8-alkylene), (C1-C8alkylene)CONR10—, (C1-C8-alkylene)NR10CO—, (C1-C8-alkylene)CONR10—(C1-C8-alkylene) or (C1-C8-alkylene)NR10CO—(C1-C8-alkylene) where R10 is hydrogen or C1-C4-alkyl; and
at least and structural units of the formula (Ib)
where A, D, R1, R2, R3 and R4 each independently have the same definitions and fulfil the same conditions as specified under the formula (Ia); and optionally,
at least one structural units of the formula (Ic):
where:
A has the same definition and fulfils the same conditions as specified under the formula (Ia); and
R11 is C1-C8-alkyl, [(C1-C8-alkylene)-O—]n—(C1-C8-alkyl) where n=1 to 12, (C1-C8-alkylene)CO2—(C1-C8-alkyl), (C1-C8-alkylene)-OCO—(C1-C8-alkyl), (C1-C8-alkylene)-OCO—(C5-C14-aryl), (C1-C8-alkylene)CO2—(C5-C14-aryl), (C1-C8-alkylene)CONR10—(C1-C8-alkyl), (C1-C8-alkylene)NR10CO—(C1-C8-alkyl), (C1-C8-alkylene)-CONR10—(C5-C14-aryl) or (C1-C8-alkylene)NR10CO—(C5-C14-aryl) where R10 is hydrogen or C1-C4-alkyl.

### Claim 2 (depends on 1)

The polymeric compound according to one or more of claims 1 further comprising at least one structural unit derived from olefins suitable for ring-opening metathesis polymerization.

### Claim 3 (depends on 1)

The polymeric compound according to claim 1, wherein A, D, M, L, X1 and X2 and R1, R2, R3, R4 and R11 radicals present in the structural units of the formulae (Ia), (Ib) and (Ic) are Identical.

### Claim 4 (depends on 1)

The polymeric compound according to claim 1, wherein the average proportion by weight of structural units of the formula (Ia) and (Ib) and (IC) present is 80% or more.

### Claim 5 (depends on 1)

The polymeric compound according to claim 1, wherein the ratio of structural units of the formula (Ia) to structural units of the formula (Ib) is 1:2 to 1:500.

### Claim 6 (depends on 1)

The polymeric compound according to claim 1, wherein the ratio of structural units of the formula (Ia) to structural units of the formula (Ic) is 10:1 to 1:200.

### Claim 7 (depends on 1)

The polymeric compound according to claim 1, wherein D in the structural units of the formulae (Ia) and (Ib) is bonded via the ortho-position to the olefin or the ylidene unit.

### Claim 8 (depends on 1)

The polymeric compound according to claim 1, wherein M in formula (Ia) is ruthenium or osmium.

### Claim 9 (depends on 1)

The polymeric compound according to claim 1, wherein B in formula (II) is 1,2-ethanediyl or 1,2-ethenediyl.

### Claim 10 (depends on 1)

The polymeric compound according to claim 1, wherein R6 and R7 in formula (II) are identical and are primary C5-C20-alkyl radicals, wherein the carbon atom bonded to the nitrogen atom bears a tertiary alkyl radical, or secondary C3-C20-alkyl radicals, tertiary C4-C20-alkyl radicals, or mono- or poly-substituted phenyl radicals wherein substitutions are in ortho-position, by C1-C4-alkyl radicals.

### Claim 11 (depends on 1)

A polymeric transition metal catalyst precursor comprising a compound of formula (IV):
where:
R1, R2, R3, R4, A and D are each as defined under formula (Ia) in claim 1.