US 6,552,139 B1 · Process for preparing acyclic olefins using homobimetallic and heterobimetallic alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands

Abstract

The invention relates to complexes of ruthenium of the structural formula I where X is an anionic ligand, Z is a monodentate to tridentate ligand which contains a metal and is nonionically bound to the ruthenium center, R1 and R2 are identical or different and are each hydrogen or/and a hydrocarbon group, but may also form a ring, and Ligand L is an N-heterocyclic carbene, and also to a process for preparing acyclic olefins having two or more carbon atoms or/and cyclic olefins having three or more carbon atoms and the use of at least one complex of the formula I in olefin metathesis.

A process for preparing acyclic olefins having two or more carbon atoms or cyclic olefins having three or more carbon atoms, in each case corresponding to the formula VI:

from acyclic olefins having two or more carbon atoms or from cyclic olefins having three or more carbon atoms, in each case corresponding to the formula VI, wherein
R′1, R′2, R′3 and R′4 in the formula VI are identical or different and are each a hydrogen atom or a hydrocarbon group,
where the hydrocarbon groups are identical or different and are independently straight-chain, branched or cyclic radicals selected from the group consisting of alkyl radicals having from 1 to 50 carbon atoms, alkenyl radicals having from 2 to 50 carbon atoms, alkynyl radicals having from 2 to 50 carbon atoms, aryl radicals having from 6 to 30 carbon atoms, metallocenyl and silyl radicals in which, at least one hydrogen is optionally replaced by a functional group, and one or more of R′1, R′2, R′3 and R′4 are optionally identical or different halo, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, sulfonyl or metallocenyl groups, or one or more pairs of R′1, R′2, R′3 and R′4 form one or more rings;
the process comprising contacting an olefin with at least one catalyst such that an olefin metathesis reaction occurs, wherein the catalyst comprises the complex of ruthenium of formula I
where X is an anionic ligand,
Z is a monodentate, bidentate or tridentate ligand which contains a metal and is nonionically bound to the ruthenium center,
R1 and R2 are identical or different and are hydrogen or a hydrocarbon group, where the hydrocarbon groups are identical or different and are each a straight-chain, branched or cyclic radical selected from the group consisting of alkyl radicals having from 1 to 50 carbon atoms, alkenyl radicals having from 2 to 50 carbon atoms, alkynyl radicals having from 2 to 50 carbon atoms, aryl radicals having from 6 to 30 carbon atoms and silyl radicals, where one or more of the hydrogen atoms in the hydrocarbon or silyl groups may be replaced by identical or independently different alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or sulfonyl groups, or R1 and R2 are identical or different and form a ring,
L is an N-heterocyclic carbene ligand having one of the formulas II-V:
where R1, R2, R3 and R4 in the formulas II, III, IV and V are identical or different and are each hydrogen or a hydrocarbon group, where the hydrocarbon groups are identical or different and are each independently cyclic, straight-chain or branched radicals selected from the group consisting of alkyl radicals having from 1 to 50 carbon atoms, alkenyl radicals having from 2 to 50 carbon atoms, alkynyl radicals having from 2 to 50 carbon atoms, and aryl radicals having from 6 to 30 atoms, in which at least one hydrogen may be replaced by a functional group and where R3 and R4 are identical or different and are each independently a halogen, nitro, nitroso, alkoxy, aryloxy, amido, carboxyl, carbonyl, thio or sulfonyl group.

6 more elements

Description4,036 words

Summary1,146 words

#1. Field of the Invention

#The invention relates to homobimetallic and heterobimetallic alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands and a process for preparing olefins from acyclic olefins having two or more carbon atoms or/and from cyclic olefins having three or more carbon atoms by olefin metathesis, in which at least one of these bimetallic alkylidene complexes is used as catalyst.

#2. Description of the Prior Art

Brief description of the drawings1 figure

#FIG. 1 is a graphic depiction of the percentage yield over time of the ring opening metathesis polymerization of 1,5-cyclooctadiene using as catalysts the following: ♦ complex 3 from the examples; ▾ complex 1 from the examples; and [Circlesolid] RuCl2(PCy3)2(CHPh).

Detailed description2,850 words

#The alkylidene complexes having the structure according to the invention and containing an N-heterocyclic carbene ligand in combination with a bidentate to tridentate ligand Z are highly active catalysts for olefin metathesis. They are particularly inexpensive. Olefin metathesis using the catalysts according to the invention displays not only a high tolerance toward a wide variety of functional groups and many possibilities for variation of the ligand sphere but also, in particular, a high activity.

#Variation of the simple-to-prepare N-heterocyclic carbene ligand L enables activity and selectivity to be controlled in a targeted way and additionally allows chirality to be introduced in a simple way. Thus, in the formulae II, III, IV and V, some or all of the hydrogen in the hydrocarbon groups R1, R2, R3 and R4 can be replaced by identical or independently different halogen atoms, in particular chlorine, bromine or iodine, or/and nitro, nitroso, hydroxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, sulfonyl, or/and metallocenyl groups.

#Examples of functional groups as substituted groups R1, R2, R3 and R4 are hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-acetylethylaminoethyl, ethoxyethyl, polyether, ethoxyacetyl, methoxycarbonylethyl, ethoxycarbonylethyl, potassium carboxylatomethyl and isopropylaminocarbonylmethy.

Facts

Application

09/488,630Filed 20 Jan 2000

Priority

DE 199 02 43922 Jan 1999

Granted

22 Apr 2003

Term ended

20 Jan 2020

Estimated · how

20 years from earliest known nonprovisional domestic filing. Maintenance-fee lapses, terminal disclaimers and statutory extensions have not been checked. The continuity chain may be incomplete; this is not an enforceability determination. Patent term adjustment is unavailable; no adjustment was added.

Classification10 codes

C07C 6/04
Metathesis reactions at an unsaturated carbon-to-carbon bond: at a carbon-to-carbon double bond
C07F 15/0046
Compounds of the platinum group: ruthenium compounds
C07C 2527/1213
Fluorides: boron fluoride
C07C 2527/122
Halogens; Compounds thereof: compounds comprising a halogen and copper

Description4,036 words

Summary1,146 words

#1. Field of the Invention

#2. Description of the Prior Art

Brief description of the drawings1 figure

Detailed description2,850 words

Process for preparing acyclic olefins using homobimetallic and heterobimetallic alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands

Life of this patent

Process for preparing acyclic olefins using homobimetallic and heterobimetallic alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands

Life of this patent

Life of this patent

Abstract

Drawings

Drawings

Claims10

Description4,036 words

Drawings

Classification10 codes

Life of this patent

Description4,036 words