Hexacoordinated ruthenium or osmium metal carbene metathesis...

Details Hexacoordinated ruthenium or osmium metal carbene metathesis... Hexacoordinated ruthenium or osmium metal carbene metathesis...

2002-06-14

2004-11-16

Harlan, Robert Deshon (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S167000, C556S014000, C556S021000, C556S022000, C556S136000, C556S137000, C526S172000, C546S002000, C546S010000, C546S012000, C544S225000, C548S101000, C548S105000, C548S106000

Reexamination Certificate

active

06818586

ABSTRACT:

BACKGROUND
Metathesis catalysts have been previously described by for example, U.S. Pat. Nos. 5,312,940, 5,342,909, 5,728,917, 5,750,815, 5,710,298, and 5,831,108 and PCT Publications WO 97/20865 and WO 97/29135 which are all incorporated herein by reference. These publications describe well-defined single component ruthenium or osmium catalysts that possess several advantageous properties. For example, these catalysts are tolerant to a variety of functional groups and generally are more active than previously known metathesis catalysts. Recently, the inclusion of an N-heterocyclic carbene (NHC) ligand, such as an imidazolidine or triazolylidene ligand as described in U.S. application Ser. Nos. 09/539,840, 09/576,370 and PCT Publication No. WO 99/51344, the contents of each of which are incorporated herein by reference, in these metal-carbene complexes has been found to improve the already advantageous properties of these catalysts. In an unexpected and surprising result, the shift in structure from the well-established penta-coordinated catalyst structure to the hexacoordinated catalyst structure has been found to significantly improve the properties of the catalyst. For example, these hexacoordinated catalysts of the present invention exhibit increased activity and selectivity not only in ring closing metathesis (“RCM”) reactions, but also in other metathesis reactions including cross metathesis (“CM”) reactions, reactions of acyclic olefins, and ring opening metathesis polymerization (“ROMP”) reactions.
SUMMARY
The present invention relates to novel hexacoordinated metathesis catalysts and to methods for making and using the same. The inventive catalysts are of the formula
wherein:
M is ruthenium or osmium;
X and X
1
are the same or different and are each independently an anionic ligand;
L, L
1′
and L
2
are the same or different and are each independently a neutral electron donor ligand; and,
R and R
1
are each independently hydrogen or a substituent selected from the group consisting of C
1
-C
20
alkyl, C
2
-C
20
alkenyl, C
2
-C
20
alkynyl, aryl, C
1
-C
20
carboxylate, C
1
-C
20
alkoxy, C
2
-C
20
alkenyloxy, C
2
-C
20
alkynyloxy, aryloxy, C
2
-C
20
alkoxycarbonyl, C
1
-C
20
alkylthio, C
1
-C
20
alkylsulfonyl, C
1
-C
20
alkylsulfinyl, and silyl. Optionally, each of the R or R
1
substituent group may be substituted with one or more moieties selected from the group consisting of C
1
-C
10
alkyl, C
1
-C
10
alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C
1
-C
5
alkyl, C
1
-C
5
alkoxy, and phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
In preferred embodiments, L
2
and L
1′
are pyridine and L is a phosphine or an N-heterocyclic carbene ligand. Examples of N-heterocyclic carbene ligands include:
wherein R, R
1
R
6
, R
7
, R
8
, R
9
, R
10
and R
11
are each independently hydrogen or a substituent selected from the group consisting of C
1
-C
20
alkyl, C
2
-C
20
alkenyl, C
2
-C
20
alkynyl, aryl, C
1
-C
20
carboxylate, C
1
-C
20
alkoxy, C
2
-C
20
alkenyloxy, C
2
-C
20
alkynyloxy, aryloxy, C
2
-C
20
alkoxycarbonyl, C
1
-C
20
alkylthio, C
1
-C
20
alkylsulfonyl, C
1
-C
20
alkylsulfinyl and silyl. Optionally, each of the R, R
1
R
6
, R
7
, R
8
, R
9
, R
10
and R
11
substituent group may be substituted with one or more moieties selected from the group consisting of C
1
-C
10
alkyl, C
1
-C
10
alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C
1
-C
5
alkyl, C
1
-C
5
alkoxy, and phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl. The inclusion of an NHC ligand to the hexacoordinated ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. Because the NHC-based hexacoordinated complexes are extremely active, the amount of catalysts that is required is significantly reduced.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention generally relates to ruthenium and osmium carbene catalysts for use in olefin metathesis reactions. More particularly, the present invention relates to hexacoordinated ruthenium and osmium carbene catalysts and to methods for making and using the same. The terms “catalyst” and “complex” herein are used interchangeably.
Unmodified ruthenium and osmium carbene complexes have been described in U.S. Pat. Nos. 5,312,940, 5,342,909, 5,728,917, 5,750,815, and 5,710,298, all of which are incorporated herein by reference. The ruthenium and osmium carbene complexes disclosed in these patents all possess metal centers that are formally in the +2 oxidation state, have an electron count of 16, and are penta-coordinated. These catalysts are of the general formula
wherein:
M is ruthenium or osmium;
X and X
1
are each independently any anionic ligand;
L and L
1
are each independently any neutral electron donor ligand;
R and R
1
are the same or different and are each independently hydrogen or a substituent selected from the group consisting of C
1
-C
20
alkyl, C
2
-C
20
alkenyl, C
2
-C
20
alkynyl, aryl, C
1
-C
20
carboxylate, C
1
-C
20
alkoxy, C
2
-C
20
alkenyloxy, C
2
-C
20
alkynyloxy, aryloxy, C
2
-C
20
alkoxycarbonyl, C
1
-C
20
alkylthio, C
1
-C
20
alkylsulfonyl, C
1
-C
20
alkylsulfinyl, and silyl. Optionally, each of the R or R
1
substituent group may be substituted with one or more moieties selected from the group consisting of C
1
-C
10
alkyl, C
1
-C
10
alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C
1
-C
5
alkyl, C
1
-C
5
alkoxy, and phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
The catalysts of the present invention are similar in that they are Ru or Os complexes; however, in these complexes, the metal is formally in the +2 oxidation state, and has an electron count of 18 and are hexacoordinated. These catalysts are of the general formula:
wherein
M is ruthenium or osmium;
X and X
1
are the same or different and are each independently any anionic ligand;
L, L
1′
, and L
2
are the same or different and are each independently any neutral electron donor ligand;
R and R
1
are the same or different and are each independently hydrogen or a substituent selected from the group consisting of C
1
-C
20
alkyl, C
2
-C
20
alkenyl, C
2
-C
20
alkynyl, aryl, C
1
-C
20
carboxylate, C
1
-C
20
alkoxy, C
2
-C
20
alkenyloxy, C
2
-C
20
alkynyloxy, aryloxy, C
2
-C
20
alkoxycarbonyl, C
1
-C
20
alkylthio, C
1
-C
20
alkylsulfonyl, C
1
-C
20
alkylsulfinyl, and silyl. Optionally, each of the R or R
1
substituent group may be substituted with one or more moieties selected from the group consisting of C
1
-C
10
alkyl, C
1
-C
10
a

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