Imidazolidine-based metal carbene metathesis catalysts
The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are wherein: M is ruthenium or osmium; X and X 1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R 1 R 6 , R 7 , R 8 , and R 9 are each independently hydrogen or a substituent selected for the group consisting of C 1 C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 alkyithiol, aryl thiol, C 1 -C 20 alkylsulfortyl and C 1 -C 20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 10 alkoxy, aryl, and a functional group. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes.
1. A composition of matter comprising a compound having the formula:
where:
M is Ru or Os;
X and X 1 are each independently an anionic ligand;
P is phosphorus;
R g , R h and R i are each independently:
(1) a C 1-10 alkyl group,
(2) a C 3-10 cycloalkyl group or
(3) a C 5-20 aryl group;
R, R 6 , R 7 , R 8 , and R 9 are each independently:
(1) hydrogen,
(2) a C 1-10 alkyl group,
(3) a C 2-20 alkenyl group,
(4) a C 2-20 alkynyl group,
(5) an aryl group,
(6) a C 1-20 carboxylate group,
(7) a C 1-20 alkoxy group,
(8) a C 2-20 alkenyloxy group,
(9) a C 2-20 alkenyloxy group,
(10) an aryloxy group,
(11) a C 2-20 alkoxycarbonyl group,
(12) a C 1-20 alkylthiol group,
(13) a C 1-20 alkylsulfonyl group,
(14) a C 1-20 alkylsulfinyl group,
where each of R, R 6 , R 7 , R 8 , and R 9 is optionally substituted with
(a) halogen,
(b) a C 1-10 alkyl group,
(c) a C 1-10 alkoxy group,
(d) an aryl group
(e) a hydroxyl group,
(f) a thiol group,
(g) a thioester group,
(h) a ketone group,
(i) an aldehyde group,
(j) an ester group,
(k) an ether group,
(l) an amino group,
(m) an amido group,
(n) an imino group,
(o) a nitro group,
(p) a carboxylic acid group,
(q) a disulfide group,
(r) a carbonate group,
(s) an isocyanate group,
(t) a carbodiimide group,
(u) a carboalkoxy group, or
(v) a carbamate group.
2. An olefin metathesis catalyst wherein the metathesis catalyst has the following structure:
wherein,
M is ruthenium or osmium;
X and X 1 are each independently an anionic ligand;
L 1 is an imidazolidine ligand;
L is a neutral electron donor ligand; and
R and R 1 are each independently hydrogen, C 1-10 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, aryl, C 1-20 carboxylate, C 1-20 alkoxy, C 2-20 alkenyloxy, C 2-20 alkynyloxy, aryloxy, C 2-20 alkoxycarbonyl, C 1-20 alkylthiol, aryl thiol, C 1-20 alkylsulfonyl, and C 1-20 alkylsulfinyl, and wherein each of R and R 1 is optionally substituted with halogen, C 1-10 alkyl, C 1-10 alkoxy, aryl, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amino, amido, imino, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, or carbamate; and
wherein at least one of L, L 1 , R, R 1 , X, and X 1 may be linked with at least one of L, L 1 , R, R 1 , X, and X 1 to form a bonded ligand array or a bidentate ligand.
3. The metathesis catalyst of claim 2 , wherein the imidazolidine ligand has the following structure:
wherein,
R 6 , R 7 , R 8 , and R 9 are each independently hydrogen, C 1-10 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, aryl, C 1-20 carboxylate, C 1-20 alkoxy, C 2-20 alkenyloxy, C 2-20 alkynyloxy, aryloxy, C 2-20 alkoxycarbonyl, C 1-20 alkylthiol, aryl thiol, C 1-20 alkylsulfonyl, and C 1-20 alkylsulfinyl, and wherein each of R 6 , R 7 , R 8 , and R 9 is optionally substituted with halogen, C 1-10 alkyl, C 1-10 alkoxy, aryl, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amino, amido, imino, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, or carbamate.
4. The metathesis catalyst of claim 2 , wherein at least one of L, L 1 , R, R 1 , X, and X 1 is linked with at least one of L, L 1 , R, R 1 , X, and X 1 to form a bonded ligand array.
5. The metathesis catalyst of claim 2 , wherein L is bonded together with one of X and X 1 to form a bidentate ligand.
6. The metathesis catalyst of claim 2 , wherein L is bonded together with one of R and R 1 to form a bidentate ligand.
7. The metathesis catalyst of claim 2 , wherein R and R 1 are bonded together.
8. The metathesis catalyst of claim 2 , wherein the metathesis catalyst has the following structure:
wherein,
M is ruthenium or osmium;
X and X 1 are each independently an anionic ligand;
L is a neutral electron donor ligand; and
R, R 1 , R 6 , R 7 , R 8 , and R 9 are each independently hydrogen, C 1-10 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, aryl, C 1-20 carboxylate, C 1-20 alkoxy, C 2-20 alkenyloxy, C 2-20 alkynyloxy, aryloxy, C 2-20 alkoxycarbonyl, C 1-20 alkylthiol, aryl thiol, C 1-20 alkylsulfonyl, and C 1-20 alkylsulfinyl, and wherein each of R and R 1 is optionally substituted with halogen, C 1-10 alkyl, C 1-10 alkoxy, aryl, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amino, amido, imino, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, or carbamate.
9. The metathesis catalyst of claim 8 , wherein at least one of L, L 1 , R, R 1 , R 8 , R 9 , X, and X 1 is linked with at least one of L, L 1 , R, R 1 , R 8 , R 9 , X, and X 1 to form a bonded, bidentate, or multidentate ligand array.
10. The metathesis catalyst of claim 8 , wherein L is bonded together with one of X and X 1 to form a bidentate ligand.
11. The metathesis catalyst of claim 8 , wherein L is bonded together with one of R and R 1 to form a bidentate ligand.
12. The metathesis catalyst of claim 8 , wherein R and R 1 are bonded together.
13. A metathesis catalyst wherein the metathesis catalyst has the following structure:
wherein,
M is Ru or Os;
X and X 1 are each independently an anionic ligand;
P is phosphorus;
R g , R h and R i are each independently:
(1) a C 1-10 alkyl group,
(2) a C 3-10 cycloalkyl group or
(3) a C 5-20 aryl group;
R, R 6 , R 7 , R 8 , and R 9 are each independently:
(1) hydrogen,
(2) a C 1-10 alkyl group,
(3) a C 2-20 alkenyl group,
(4) a C 2-20 alkynyl group,
(5) an aryl group,
(6) a C 1-20 carboxyiate group,
(7) a C 1-20 alkoxy group,
(8) a C 2-20 alkenyloxy group,
(9) a C 2-20 alkynyloxy group,
(10) an aryloxy group,
(11) a C 2-20 alkoxycarbonyl group,
(12) a C 1-20 alkylthiol group,
(13) a C 1-20 alkylsulfonyl group,
(14) a C 1-20 alkylsulfinyl group,
where each of R, R 6 , R 7 , R 8 , and R 9 is optionally substituted with
(a) halogen,
(h) a C 1-10 alkyl group,
(c) a C 1-10 alkoxy group,
(d) an aryl group
(e) a hydroxyl group,
(f) a thiol group,
(g) a thioester group,
(h) a ketone group,
(i) an aldehyde group,
(j) an ester group,
(k) an ether group,
(l) an amino group,
(m) an amido group,
(n) an imino group,
(o) a nitro group,
(p) a carboxylic acid group,
(q) a disulfide group,
(r) a carbonate group,
(s) an isocyanate group,
(t) a carbodiimide group,
(u) a carboalkoxy group, or
(v) a carbamate group.