Carbene transition metal catalysts

• US 6,313,331 B1
• Filed: 02/25/2000
• Issued: 11/06/2001
• Est. Priority Date: 12/18/1998
• Status: Expired due to Fees

• Current Assignee: The Governors of the University of Alberta (University of Alberta)
• Original Assignee: The Governors of the University of Alberta (University of Alberta)
• Inventors: Wang, Qinyan, Cavell, Ronald G., Kasani, Aparna, Babu, Ruppa P. Kamalesh
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US09/513,682
• Time in Patent Office: 620 Days
• Field of Search: 556/1, 556/18, 556/22, 556/42, 556/52, 556/58, 556/121, 556/140, 534/15, 502/103, 502/117, 526/131, 526/160, 526/161
• US Class Current: 556/18
• CPC Class Codes: C07F 9/5355 Phosphoranes containing the structure P=N-
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 4/52 selected from boron, aluminium, gallium, indium, thallium or rare earths C08F4/14 takes precedence
• CPC Class Codes: C08F 4/659 Component covered by group C08F4/64 containing a transition metal-carbon bond C08F4/64003 - C08F4/64196 take precedence
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer

Abstract

The present invention relates to novel complexes of (transition) metals containing ligands having phosphorus centers supporting a carbene structure or heteroalkane radical bonded to the (transition) metal.

Claims

1. A complex of the formula II:

wherein M is a metal atom selected from the group consisting of a transition metal, a post transition metal and a lanthanide;

R¹, R², R³ and R⁴ are independently selected from the group consisting of a hydrogen atom, a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom and a C_1-6 alkyl radical;

R⁷ and R⁸ are independently selected from the group consisting of a halogen atom, an alkyl, an amide —

NR¹R², an alkoxide or aryl oxide group —

OR¹, and an —

OSi(R¹)₃ group wherein R¹ and R² are defined above, a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which are unsubstituted or substituted by a halogen atom or a C_1-6 alkyl radical, and a Lewis base which may contain a donor heteroatom, and each R⁵ is independently selected from the group consisting of radicals selected from the group consisting of saturated and unsaturated straight chained, branched and cyclic hydrocarbyl radicals, C_6-12 cyclic aliphatic or aromatic radical;

radicals of the formula Si(R⁶)₃ wherein each R⁶ is independently selected from the group consisting of saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals, and radicals of the formula III;

wherein R⁹, R¹⁰, R¹¹ and R¹² are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a NO₂ radical, a C_1-6 alkyl radical, and a C_8-12 aryl radical and E is an endocyclic nitrogen atom or a C—

CN group and R¹⁴ is selected from the group consisting of a hydrogen atom and a C_1-20 hydrocarbyl radical which may contain a terminal functional group; and

optionally R¹⁴ taken together with the transitional metal may form a constrained ring.

2. The complex according to claim 1, wherein M is selected from the group consisting of Y, Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd, Zn and Sm.

3. The complex according to claim 2, wherein R¹, R², R³ and R⁴ are selected from the group consisting of C_1-10 straight chained, branched or cyclic alkyl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of a chlorine atom, a fluorine atom and a C_1-4 alkyl radical and C_5-14 aromatic radicals which are unsubstituted or further substituted by up to n-1, wherein n is the number of carbon atoms in the aromatic radical substituents selected from the group consisting of a fluorine atom, a chlorine atom and a C_1-6 alkyl radical or an amido radical which is unsubstituted or substituted by up to two C_1-6 alkyl radicals.

4. The complex according to claim 3, wherein R⁷ and R⁸ are selected from the group consisting of a chlorine atom, a fluorine atom, a C_1-10 straight chained, branched or cyclic alkyl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of a chlorine atom, a fluorine atom and a C_1-4 alkyl radical;

an amide of the formula —

NR¹R² where in R¹ and R² are C_1-4 alkyl radicals;

C_5-14 aromatic radicals which are unsubstituted or further substituted by up to n-1, wherein n is the number of carbon atoms in the aromatic radical substituents selected from the group consisting of a fluorine atom, a chlorine atom and a C_1-6 alkyl radical or an amido radical which is unsubstituted or substituted by up to two C_1-6 alkyl radicals;

C_1-6 alkyl ethers, C_4-8 cyclic ethers;

C_1-6 tertiary amines;

cyclic C_4-8 nitrogen containing compounds; and

tertiary C_1-10 phosphines.

5. A complex according to claim 4, wherein R¹⁴ is selected from the group consisting of C_1-8 alkyl radicals or C_6-10 aromatic radicals which may have a terminal function group and further proved that R¹⁴ together with M may for a constrained ring.

6. The complex according to claim 5, wherein R¹, R², R³ and R⁴ are selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a methyl radical, an ethyl radical, a propyl radical, a butyl radical, a tertiary butyl radical and a phenyl radical.

7. The complex according to claim 6, wherein one or more R⁵ substituents are selected from the group consisting of C_1-6 alkyl radicals and C_6-12 cyclic aliphatic or aromatic radicals.

8. The complex according to claim 7, wherein R⁵ is selected from the group consisting of methyl, ethyl, butyl, phenyl and adamantyl radicals.

9. The complex according to claim 6, wherein one or more R⁵ substituents is a radical of the formula III:

wherein R⁹, R¹⁰, R¹¹ and R¹² are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a NO₂ radical, a C_1-6 alkyl radical, and a C_8-12 aryl radical and E is an endocyclic nitrogen atom or a C—

CN group.

10. The complex according to claim 9, wherein E is an endocyclic nitrogen atom.

11. The complex according to claim 9, wherein E is a C—

CN group.

12. The complex according to claim 11, wherein one or more R⁵ substituents is a 4-cyanotetrafluorophenyl radical.

13. The complex according to claim 6, wherein one or more R⁵ substituents is selected from the group consisting of radicals of the formula Si(R⁶)₃ wherein each R⁶ is independently selected from the group consisting of C_1-10 saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals.

14. The complex according to claim 13, wherein R⁶ is selected from the group consisting of methyl, ethyl, propyl and butyl radicals.

15. A complex of the formula V:

wherein M is a metal atom selected from the group consisting of a transition metal, a post transition metal and a lanthanide;

R¹, R², R³ and R⁴ are independently selected from the group consisting of a hydrogen atom, a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom and a C_1-6 alkyl radical; and

each R⁵ is independently selected from the group consisting of radicals selected from the group consisting of saturated and unsaturated straight chained, branched and cyclic hydrocarbyl radicals, C_6-12 cyclic aliphatic or aromatic radical;

radicals of the formula Si(R⁶)₃ wherein each R⁶ is independently selected from the group consisting of saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals, and radicals of the formula III;

wherein R⁹, R¹⁰, R¹¹ and R¹² are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a NO₂ radical, a C_1-6 alkyl radical, and a C_8-12 aryl radical and E is an endocyclic nitrogen atom or a C—

CN group.

16. The complex according to claim 15, wherein M is selected from the group consisting of Y, Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd, Zn and Sm.

17. The complex according to claim 16, wherein R¹, R², R³ and R⁴ are selected from the group consisting of C_1-10 straight chained, branched or cyclic alkyl radicals which are unsubstituted or substituted by up to three substituents selected from the group consisting of a chlorine atom, a fluorine atom and a C_1-4alkyl radical and C_5-14 aromatic radicals which are unsubstituted or further substituted by up to n-1, wherein n is the number of carbon atoms in the aromatic radical substituents selected from the group consisting of a fluorine atom, a chlorine atom and a C_1-6 alkyl radical or an amido radical which is unsubstituted or substituted by up to two C_1-6 alkyl radicals.

18. The complex according to claim 17, wherein R¹, R², R³ and R⁴ are selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a methyl radical, an ethyl radical, a propyl radical, a butyl radical, a tertiary butyl radical and a phenyl radical.

19. The complex according to claim 18, wherein one or more R⁵ substituents are selected from the group consisting of C_1-6 alkyl radicals and C_6-12 cyclic aliphatic or aromatic radicals.

20. The complex according to claim 19, wherein R⁵ is selected from the group consisting of methyl, ethyl, butyl, phenyl and adamantyl radicals.

21. The complex according to claim 18, wherein one or more R⁵ substituents is a radical of the formula III:

wherein R⁹, R¹⁰, R¹¹ and R¹² are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a NO₂ radical, a C_1-6 alkyl radical, and a C_8-12 aryl radical and E is an endocyclic nitrogen atom or a C—

CN group.

22. The complex according to claim 21, wherein E is an endocyclic nitrogen atom.

23. The complex according to claim 21, wherein E is a C—

CN group.

24. The complex according to claim 23, wherein one or more R⁵ substituents is a 4-cyanotetrafluorophenyl radical.

25. The complex according to claim 18, wherein one or more R⁵ substituents are selected from the group consisting of radicals of the formula Si(R⁶)₃ wherein each R⁶ is independently selected from the group consisting of C_1-10 saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals.

26. The complex according to claim 25, wherein R⁶ is selected from the group consisting of methyl, ethyl, propyl and butyl radicals.