Immobilized metathesis tungsten oxo alkylidene catalysts and use thereof in olefin metathesis

1. A tungsten catalyst comprising (≡SiO) X W(═O)(═(CR 1 R 2 )(R 3 or R 4 ) 2-x (L) z , wherein (≡SiO) X is comprised in a solid support, wherein each of R 1 and R 2 is independently R, —OR, —SR, —N(R) 2 , —OC(O)R, —SOR, —SO 2 R 1 , —SO 2 N(R) 2 , C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R;

each R is independently hydrogen or an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 4-7membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms in- dependently selected from nitrogen, oxygen, or sulfur, or:

two R groups on the same nitrogen atom are taken together with the nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated, or aryl ring having 0-5 additional heteroatoms not including the same nitrogen atom independently selected from nitrogen, oxygen, or sulfur; or:

two R groups on the same oxygen atom are taken together with the oxygen to form an optionally substituted 3-12 membered saturated, partially unsaturated, or aryl ring having 0-5 additional heteroatoms not including the same oxygen atom independently selected from nitrogen, oxygen, or sulfur;

R 3 and R 4 have independently the same meaning as R 1 and R 2 ; or tris(C 1-20 alkyl)silyl, tris(C 1-20 alkyl)silyloxy, tris(C 1-20 alkoxy)silyl, tris(C 1-20 alkoxy)silyloxy, tris(aryl)silyl, tris(aryl)silyloxy, tris(aryloxy)silyl, or tris(aryloxy)silyloxy; and

wherein x=1 or 2;

z=0, 1 or 2 or a number between 0 and 2;

and L is a neutral ligand.

2. A tungsten catalyst comprising (≡SiO) X W(═O)(═(CR 1 R 2 )(R 3 or R 4 ) 2-x (L) z wherein (≡SiO) X is comprised in a solid support, wherein each of R 1 and R 2 is independently R, —OR, —SR, —N(R) 2 , —OC(O)R, —SOR, —SO 2 R, —SO 2 N(R) 2 , C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R;

each R is independently hydrogen or an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms in- dependently selected from nitrogen, oxygen, or sulfur, or:

two R groups on the same nitrogen atom are taken together with the nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated, or aryl ring having 0-5 additional heteroatoms not including the same nitrogen atom independently selected from nitrogen, oxygen, or sulfur; or:

two R groups on the same oxygen atom are taken together with the oxygen to form an optionally substituted 3-12 membered saturated, partially unsaturated, or aryl ring having 0-5 additional heteroatoms not including the same oxygen atom independently selected from nitrogen, oxygen, or sulfur;

R 3 and R 4 have independently the same meaning as R 1 and R 2 ; or tris(C 1-20 alkyl)silyl, tris(C 1-20 alkyl)silyloxy, tris(C 1-20 alkoxy)silyl, tris(C 1-20 alkoxy)silyloxy, tris(aryl)silyl, tris(aryl)silyloxy, tris(aryloxy)silyl, or tris(aryloxy)silyloxy; and

wherein x=1 or 2;

z=0, 1 or 2 or a number between 0 and 2;

and L is a neutral ligand,

prepared according a method comprising at least the following step (i):

(i) reacting silica (SiO 2 ) with a tungsten oxo alkylidene complex comprising (R 3 )(R 4 )W(═O)(═CR 1 R 2 )(L) y , wherein y=0, 1, or 2, wherein L, R 1 , R 2 , R 3 and R 4 have the meaning as defined above, and wherein R 3 and R 4 additionally may independently be Cl.

3. A method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising step (i):

(i) reacting the first olefin with the second olefin in the presence of the catalyst of claim 1 .

4. The method of claim 3 , wherein

(a) the first olefin has a terminal olefinic double bond, and the second olefin has a terminal olefinic double bond, wherein the first and the second olefin are identical [homo or self-metathesis (SM)]; or

(b) the first and the second olefin are different from one another [cross metathesis (CM)]; or

(c) the first olefin has an internal olefinic double bond and the second olefin is ethylene [ethenolysis]; or

(d) the first olefin is a cyclic olefin and the second olefin is a cyclic olefin, wherein the first and the second olefin may be identical or may be different from one another [cross metathesis (CM)]; or

(e) the first olefin is a diene and the second olefin is a diene, wherein the first olefin and the second olefin are identical, wherein step (i) results in ring closing of the diene [ring closing metathesis (RCM)]; or

(f) the first olefin is a cyclic olefin and the second olefin is a cyclic olefin, wherein the first olefin and the second olefin are identical, wherein step (i) results in a ring opening metathesis polymerization (ROMP); or

(g) the first olefin is a cyclic olefin and the second olefin is a cyclic olefin, wherein the first olefin and the second olefin are identical, wherein step (i) results in a ring opening metathesis followed by a ring-closing metathesis reaction (ROM-RCM); or

(h) the first olefin is a terminal diene and the second olefin is a terminal diene, wherein the first olefin and the second olefin are identical, and wherein step (i) results in an acyclic diene metathesis polymerization (ADMET), wherein a polyene and ethylene are generated.

5. The method of claim 3 , further comprising at least step (ii) or steps (ii) and (iii):

(ii) separating the catalyst from the reaction mixture obtained in step (i), by filtration, centrifugation, or distillation;

(iii) re-using the catalyst obtained in step (ii).

6. The tungsten catalyst of claim 1 , wherein ═CR 1 R 2 is selected from ═CHC(CH 3 ) 3 or ═CHC(CH 3 ) 2 C 6 H 5 .

7. The tungsten catalyst of claim 1 , wherein R 3 and R 4 are independently pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, 2,5-diphenylpyrrol-1-yl, or —OR, wherein R is a six membered or 10 membered aryl ring.

8. The tungsten catalyst of claim 7 , wherein R is a phenyl ring or an annelated phenyl ring substituted with one or more of: C 1-4 alkyl, C 1-4 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, halogen.

9. The tungsten catalyst of claim 1 , wherein ═CR 1 R 2 is selected from ═CHC(CH 3 ) 3 or ═CHC(CH 3 ) 2 C 6 H 5 and wherein R 3 ═R 4 ═—OR, wherein R is a phenyl ring or an annelated phenyl ring substituted with one or more of: C 1-4 alkyl, C 1-4 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, halogen;

or

wherein ═CR 1 R 2 is selected from ═CHC(CH 3 ) 3 or ═CHC(CH 3 ) 2 C 6 H 5 and wherein R 3 ═—OR, wherein R is a phenyl ring or an annelated phenyl ring substituted with one or more of: C 1-4 alkyl, C 1-4 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, halogen; and R 4 ═pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl;

or

wherein ═CR 1 R 2 is selected from ═CHC(CH 3 ) 3 or ═CH(C(CH 3 ) 2 C 6 H 5 and R 3 ═R 4 ═pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl.

10. The tungsten catalyst of claim 2 , wherein in step (i) SiO 2-(700) is reacted with (ArO) 2 W(═O)(═CHC(CH 3 ) 3 ) to yield [(≡SiO)W(═O)(═CHC(CH 3 ) 3 )OR] (Ar=2,6- dimesitylphenyl); or

wherein in step (i) SiO 2-(700) is reacted with (ArO)(Me 2 py)W(═O)(═CHtBu) to yield [(≡SiO)W(═O)(═CHtBu)(Me 2 py)] (Ar=2,6-dimesitylphenyl); Me 2 py=2,5-dimethylpyrrol-1-yl); or

wherein in step (i) SiO 2-(700) is reacted with (ArO)(Ph 2 py)W(═O)(═CHtBu) to yield [(≡SiO)W(═O)(═CHtBu)(Ph 2py )] (Ar=2,6-dimesitylphenyl); Ph 2 py=2,5-diphenylpyrrol-1-yl).

11. The tungsten catalyst of claim 1 , wherein the solid support further comprises Al 2 O 3 , ZrO 2 , TiO 2 , V 2 O 5 , MoO 2 , WO 3 , a silicate, a zeolite, a sulfate of an alkali metal, a phosphate of an alkali metal, a sulfate of an earth alkali metal, or a phosphate of an earth alkali metal.

12. The tungsten catalyst of claim 2 , wherein the solid support further comprises Al 2 O 3 , ZrO 2 , TiO 2 , V 2 O 5 , MoO 2 , WO 3 , a silicate, a zeolite, a sulfate of an alkali metal, a phosphate of an alkali metal, a sulfate of an earth alkali metal, or a phosphate of an earth alkali metal.

13. A method of making the tungsten catalyst of claim 1 , comprising at least the following step (i):

(i) reacting silica (SiO 2 ) comprised in the solid support with a tungsten oxo alkylidene complex comprising (R 3 )(R 4 )W(═O)(═CR 1 R 2 )(L) y , wherein y=0, 1 or 2, wherein each of R 1 and R 2 is independently R, —OR, —SR, —N(R) 2 ,—OC(O)R, —SOR, —SO 2 R, —SO 2 N(R) 2 , C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R;

each R is independently hydrogen or an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroalishatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, phenyl, ferrocene, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 4-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms in- dependently selected from nitrogen, oxygen, or sulfur, or:

two R groups on the same nitrogen atom are taken together with the nitrogen to form an optionally substituted 3-12 membered saturated, partially unsaturated, or aryl ring having 0-5 additional heteroatoms not including the same nitrogen atom independently selected from nitrogen, oxygen, or sulfur; or:

two R groups on the same oxygen atom are taken together with the oxygen to form an optionally substituted 3-12 membered saturated, partially unsaturated, or aryl ring having 0-5 additional heteroatoms not including the same oxygen atom independently selected from nitrogen, oxygen, or sulfur;

R 3 and R 4 have independently the same meaning as R 1 and R 2 , or halogen, or tris(C 1-20 alkyI)silyl, tris(C 1-20 alkyl)silyloxy, tris(C 1-20 alkoxy)silyl, tris(C 1-20 alkoxy)silyoxy, tris(aryl)silyl, tris(aryl)silyloxy, tris(aryloxy)silyl, or tris(aryloxy)silyloxy; and

L is a neutral ligand.

14. The method of claim 13 , comprising at least step (0.1) prior to step (i):

(0.1) heating the silica or heating the silica in vacuo.

15. The method of claim 13 , wherein the silica comprises SiO 2-(700) .

16. The method of claim 13 , wherein the tungsten oxo alkylidene complex used in step (i) is of formula

(R 3 )(R 4 )(W═O)(═CR 1 R 2 )

wherein

each of R 3 and R 4 has independently the meaning of R or —OR or —N(R) 2 or halogen;

and the resulting tungsten catalyst comprises

(≡SiO) X W(═O)(═(CR 1 R 2 )(R 3 or R 4 ) 2-x .

17. The method of claim 13 , wherein ═CR 1 R 2 is selected from ═CHC(CH 3 ) 3 or ═CHC(CH 3 ) 2 C 6 H 5 .