| 3661898 | May, 1972 | Dehnert et al. | 260/240G |
| WO/2000/020427 | April, 2000 | POLYMERISATION CATALYSTS | ||
| WO/2001/010875 | February, 2001 | METAL COMPLEXES COMPRISING A 2,6-DIACYLPYRIDINE-LIGAND AND THEIR USE IN THE POLYMERIZATION OF ETHYLENE | ||
| WO/2003/054038 | July, 2003 | CATALYST COMPOSITION AND OLEFIN POLYMERIZATION USING SAME | ||
| WO/2004/007509 | January, 2004 | LATE TRANSITION METAL CATALYSTS FOR OLEFIN POLYMERIZATION AND OLIGOMERIZATION |
Luks et al., “The Template Synthesis and Characterization of New Mono- and Dinuclear Podand Schiff Base Complexes of Scandium Group Elements”, Collect. Czech. Chem. Commun, 1998, vol. 63, pp. 371-377.
Pritchard et al., “Isolation of ternary complex precursors and partially condensed intermediates to macrocyclic complexes of nickel(II) and copper(II)”, Transition Metal Chemistry (London), 1998, vol. 23, pp. 609-613.
Gebbink et al., “Oxidatively Robust Monophenolate-Copper(II) Complexes as Potential Models of Galactose Oxidase”, Chem. Commun, 2003, pp. 630-631.
Bardwell et al., “The Coordination Chemistry of Mixed Pyridine-Phenol and Phenanthroline-Phenol Ligands; Synthesis and Crystal Structure of [PdL1Cl] (CH2Cl2) [HL1=6-(2-Hydroxyphenyl)-2,2′-Bipyridine]”, Polyhedron, vol. 12, No. 13, pp. 1577-1580, 1993.
Jensen et al., “Biomimetic Aryl Hydroxylation Derived from Alkyl Hydroperoxide at a Nonheme Iron Center. Evidence for an FeIV=O Oxidant”, J. Am. Chem. Soc. 2003, vol. 125, pp. 2113-2128.
1. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
2. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
3. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
4. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
5. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
6. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
7. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
8. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
9. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
10. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
11. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
12. A process to polymerize or oligomerize an unsaturated monomer comprising contacting the monomer with a transition metal catalyst compound represented by the formula:
13. The process of claim 6 wherein M is titanium, zirconium or hafnium.
14. The process of claim 1 wherein L′ is selected from the group consisting of acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride, ethylene, propylene, butene, octene, and styrene.
15. The process of claim 2 where w is equal to 1 and X is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl, phenethyl, tolyl, and allyl.
16. The process of claim 1 further comprising an activator.
17. The process of claim 2 further comprising an activator.
18. The process of claim 3 further comprising an activator.
19. The process of claim 4 further comprising an activator.
20. The process of claim 5 further comprising an activator.
21. The process of 6 further comprising an activator.
22. The process of 7 further comprising an activator.
23. The process of claim 8 further comprising an activator.
24. The process of claim 8 further comprising an activator.
25. The process of claim 9 further comprising an activator.
26. The process of claim 10 further comprising an activator.
27. The process of claim 11 further comprising an activator.
28. The process of claim 12 further comprising an activator.
29. The process of claim 16 wherein the activator comprises an alumoxane.
30. The process of claim 1 wherein the transition metal catalyst compound is present on a support.
31. The process of claim 30 wherein the support is silica.
32. The process of claim 1 wherein each R1 and R2 is, independently, selected from the group consisting of cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl, dimethylphenyl, diethylphenyl, anthracenyl, adamantyl, norbornyl, and naphthyl.
33. The process of claim 2 wherein each R1 and R2 is, independently, selected from the group consisting of cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl, dimethylphenyl, diethylphenyl, anthracenyl, adamantyl, norbornyl, and naphthyl.
34. The process of claim 3 wherein each R1 and R2 is, independently, selected from the group consisting of cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl, dimethylphenyl, diethylphenyl, anthracenyl, adamantyl, norbornyl, and naphthyl.
35. The process of claim 4 wherein each R1 and R2 is, independently, selected from the group consisting of cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl, dimethylphenyl, diethylphenyl, anthracenyl, adamantyl, norbornyl, and naphthyl.
36. The process of claim 5 wherein each R1 and R2 is, independently, selected from the group consisting of cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl, dimethylphenyl, diethylphenyl, anthracenyl, adamantyl, norbornyl, and naphthyl.
37. The process of claim 6 wherein each R1 and R2 is, independently, selected from the group consisting of cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl, dimethylphenyl, diethylphenyl, anthracenyl, adamantyl, norbornyl, and naphthyl.
FIELD OF THE INVENTION
This invention relates to catalyst compounds useful for polymerization and or oligomerization of unsaturated monomers, such as olefins.
BACKGROUND OF THE INVENTION
As is well known, various processes and catalysts exist for the homopolymerization or copolymerization of olefins.
New polymerization catalysts are of great interest in the industry because they offer many new opportunities for providing new processes and products to the markets in a cheaper and more efficient manner. The following invention relates to new polymerization technology based upon new late transition metal catalyst compounds.
References of general interest related to the instant invention include:
WO 2000/020427; WO 2001/010875; WO 2003/054038; Polymer International, (2002) 51 (12), 1301-1303; Collection of Czechoslovak Chemical Communications (1988), 63(3), 371-377; and Transition Metal Chemistry (London) (1988) 23 (5), 609-613.
SUMMARY OF THE INVENTION
The present invention is directed toward Group 4, 5, 6, 7, 8, 9, 10 or 11 transition metal compounds containing neutral, mono- or di-anionic tridentate nitrogen/oxygen based ligands that are useful, with or without activators, to polymerize olefins, particularly α-olefins, or other unsaturated monomers. For the purposes of this disclosure, “α-olefins” includes ethylene.
The present invention is also directed toward Group 4, 5, 6, 7, 8, 9, 10 or 11 transition metal compounds containing neutral, bidentate nitrogen/oxygen based ligands that are useful, with or without activators, to polymerize olefins, particularly α-olefins, or other unsaturated monomers.
The oligomerization or polymerization compositions of this invention preferably comprise transition metal compounds of formula: [LMX w ] z wherein
-
- w is 1, 2 or 3;
- z is 1 or 2;
- each M is, independently, a Group 4 to 11 metal, preferably a Group 4, 7, 8, 9, or 10 metal;
- each L is, independently, a neutral, mono- or di-anionic tridentate ligand that is bonded to M by two nitrogen atoms and one oxygen atom, (where one of the nitrogen atoms and the oxygen atom are terminal atoms and the other nitrogen atom is a central atom), and the central nitrogen atom is part of a pyridinyl ring, and the central nitrogen atom is connected to the terminal oxygen atom at one ortho position of the pyridinyl ring via a group having at least two carbon atoms, and the central nitrogen atom is connected to the terminal nitrogen atom at the other ortho position of the pyridinyl ring via a group having at least one carbon atom (preferably at least two carbon atoms), and the terminal nitrogen atom is substituted with one C 3 -C 50 hydrocarbyl or one hydrogen or substituted with one C 3 -C 50 hydrocarbyl and one hydrogen atom or two hydrocarbyls wherein at least one hydrocarbyl is a C 3 -C 50 hydrocarbyl, and the terminal oxygen atom is bonded to two different carbon atoms or one carbon atom and one hydrogen atom to give a neutral donor or one carbon atom to form a mono-anionic donor; and
- X is independently a monoanionic ligand.
The oligomerization or polymerization compositions of this invention also preferably comprises transition metal compounds of formula: [LMX w ] z wherein
-
- w is 1, 2 or 3;
- z is 1 or 2;
- each M is, independently, a Group 4 to 11 metal, preferably a Group 4, 7, 8, 9, or 10 metal;
- each L is, independently, a neutral bidentate ligand that is bonded to M by two nitrogen atoms, (where one of the nitrogen atoms is a terminal atom and the other nitrogen atom is a central atom), and the central nitrogen atom is part of a pyridinyl ring and the central nitrogen atom is connected to the terminal nitrogen atom at one ortho position of the pyridinyl ring via a group having at least one carbon atom (preferably at least two carbon atoms), and the other ortho position of the pyridyl ring is substituted with a group represented by the formula —CR═CR—O—R, wherein each R is independently a C1 to C12 alkyl group, and the terminal nitrogen atom is substituted with one C 3 -C 50 hydrocarbyl or one hydrogen or substituted with one C 3 -C 50 hydrocarbyl and one hydrogen atom or two hydrocarbyls wherein at least one hydrocarbyl is a C 3 -C 50 hydrocarbyl; and
- X is independently a monoanionic ligand.
This invention further relates to transition metal compounds represented by formulae 1 to 6.
wherein
- each M is, independently, a group 4, 5, 6, 7, 8, 9, 10, or 11 transition metal;
- N is nitrogen;
- O is oxygen;
- each X is, independently, an anionic monodentate ligand;
- w is 1, 2 or 3;
- each R is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
- each R 1 and R 2 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, or independently, may join together to form a cyclic or polycyclic ring structure;
- each R 3 , R 4 , R 5 , is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, or independently, may join together to form a cyclic or polycyclic ring structure;
- each R 6 is, independently, a hydrogen, a C 3 to C 50 hydrocarbyl or a C 3 to C 50 halocarbyl;
- each R 7 is, independently, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
- each R 8 is, independently, a hydrogen, a C 3 to C 50 hydrocarbyl or a C 3 to C 50 halocarbyl;
- each x is, independently, 1, 2, 3 or 4;
- each R 9 is, independently, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
- and L′ is a neutral ligand bonded to M, and
- m is 0, 1 or 2.
wherein
- each M is, independently, a group 4, 5 or 6 transition metal;
- N is nitrogen;
- O is oxygen;
- each X is, independently, an anionic monodentate ligand,
- w is 1 2, or 3;
- each R is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
- each R 1 and R 2 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, or independently, may join together to form a cyclic or polycyclic ring structure;
- each R 3 , R 4 , R 5 , is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, or independently, may join together to form a cyclic or polycyclic ring structure;
- each R 6 is, independently, a hydrogen, a C 3 to C 50 hydrocarbyl or a C 3 to C 50 halocarbyl;
- each R 7 is, independently, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
- each R 8 is, independently, a hydrogen, a C 3 to C 50 hydrocarbyl or a C 3 to C 50 halocarbyl;
- each x is, independently, 1, 2, 3 or 4;
- and L′ is a neutral ligand bonded to M, and
- m is 0, 1 or 2.
In the formulae depicted throughout this specification and the claims, a solid line indicates a bond, and an arrow indicates that the bond may be dative.
This invention further relates to a process to oligomerize or polymerize an unsaturated monomer using the compositions described herein.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a drawing of the molecular structure of compound 4a.
FIG. 2 is a drawing of the molecular structure of compound 5a.
FIG. 3 is a drawing of the molecular structure of compound 5c.
FIG. 4 is a drawing of the molecular structure of compound 8a.
FIG. 5 is a drawing of the molecular structure of compound 8c.
FIG. 6 is a drawing of the molecular structure of compound 8d.
DEFINITIONS
As used herein, the new notation for the Periodic Table Groups is used as described in C
Neutral ligands are defined as ligands that are neutral, with respect to charge, when formally removed from the metal in their closed shell electronic state. Neutral ligands contain at least one lone pair of electrons, pi-bond or sigma bond that are capable of binding to the transition metal. Neutral ligands may also be polydentate when more than one Neutral ligand is connected via a bond or a hydrocarbyl, substituted hydrocarbyl or a functional group tether. A Neutral ligand may be a substituent of another metal complex, either the same or different, such that multiple complexes are bound together.
Anionic ligands are defined as ligands that are anionic, with respect to charge, when formally removed from the metal in their closed shell electronic state. Anionic ligands include hydride, halide, hydrocarbyl, substituted hydrocarbyl or functional group. Non-limiting examples of anionic ligands include hydride, fluoride, chloride, bromide, iodide, alkyl, aryl, alkenyl, alkynyl, allyl, benzyl, acyl, trimethylsilyl. Anionic ligands may also be polydentate when more than one anionic ligand is connected via a bond or a hydrocarbyl, substituted hydrocarbyl or a functional group tether. An anionic ligand may be a substituent of another metal complex, either the same or different, such that multiple complexes are bound together. A mono-anionic ligand is defined to be an anionic ligand that has a −1 charge. A di-anionic ligand is defined to be an anionic ligand that has a −2 charge.
The terms “hydrocarbyl radical,” “hydrocarbyl” and hydrocarbyl group” are used interchangeably throughout this document. Likewise the terms “group” and “substituent” are also used interchangeably in this document. For purposes of this disclosure, “hydrocarbyl radical” is defined to be C 1 -C 100 radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic, and include substituted hydrocarbyl radicals, halocarbyl radicals, and substituted halocarbyl radicals, silylcarbyl radicals, and germylcarbyl radicals as these terms are defined below.
Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with at least one functional group such as NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SiR* 3 , GeR* 3 , SnR* 3 , PbR* 3 and the like or where at least one non-hydrocarbon atom or group has been inserted within the hydrocarbyl radical, such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR* 2 , GeR* 2 , SnR* 2 , PbR* 2 and the like, where R* is independently a hydrocarbyl or halocarbyl radical.
Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen (e.g. F, Cl, Br, I) or halogen-containing group (e.g. CF 3 ).
Substituted halocarbyl radicals are radicals in which at least one halocarbyl hydrogen or halogen atom has been substituted with at least one functional group such as NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SiR* 3 , GeR* 3 , SnR* 3 , PbR* 3 and the like or where at least one non-carbon atom or group has been inserted within the halocarbyl radical such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR* 2 , GeR* 2 , SnR* 2 , PbR* 2 and the like where R* is independently a hydrocarbyl or halocarbyl radical provided that at least one halogen atom remains on the original halocarbyl radical.
Silylcarbyl radicals (also called silylcarbyls) are groups in which the silyl functionality is bonded directly to the indicated atom or atoms. Examples include SiH 3 , SiH 2 R*, SiHR* 2 , SiR* 3 , SiH 2 (OR*), SiH(OR*) 2 , Si(OR*) 3 , SiH 2 (NR* 2 ), SiH(NR* 2 ) 2 , Si(NR* 2 ) 3 , and the like where R* is independently a hydrocarbyl or halocarbyl radical as defined above and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.
Germylcarbyl radicals (also called germylcarbyls) are groups in which the germyl functionality is bonded directly to the indicated atom or atoms. Examples include GeH 3 , GeH 2 R*, GeHR* 2 , GeR 5 3 , GeH 2 (OR*), GeH(OR*) 2 , Ge(OR*) 3 , GeH 2 (NR* 2 ), GeH(NR* 2 ) 2 , Ge(NR* 2 ) 3 , and the like where R* is independently a hydrocarbyl or halocarbyl radical as defined above and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.
Polar radicals or polar groups are groups in which the heteroatom functionality is bonded directly to the indicated atom or atoms. They include heteroatoms of groups 1-17 of the periodic table either alone or connected to other elements by covalent or other interactions such as ionic, van der Waals forces, or hydrogen bonding. Examples of functional groups include carboxylic acid, acid halide, carboxylic ester, carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen (Group 14) analogues, alcohol and phenol, ether, peroxide and hydroperoxide, carboxylic amide, hydrazide and imide, amidine and other nitrogen analogues of amides, nitrile, amine and imine, azo, nitro, other nitrogen compounds, sulfur acids, selenium acids, thiols, sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphorus compounds, silanes, boranes, borates, alanes, aluminates. Functional groups may also be taken broadly to include organic polymer supports or inorganic support material such as alumina, and silica. Preferred examples of polar groups include NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SnR* 3 , PbR* 3 and the like where R* is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl radical as defined above and two R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.
In some embodiments, the hydrocarbyl radical is independently selected from methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also included are isomers of saturated, partially unsaturated and aromatic cyclic structures wherein the radical may additionally be subjected to the types of substitutions described above. Examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and the like. For this disclosure, when a radical is listed, it indicates that radical type and all other radicals formed when that radical type is subjected to the substitutions defined above. Alkyl, alkenyl and alkynyl radicals listed include all isomers including where appropriate cyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and analogous substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cyclic compound having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.
In the context of this document, “homopolymerization” would produce a polymer made from one monomer. For example, homopolymerization of propylene would produce homopolypropylene, also called polypropylene. Homopolymerization of ethylene would produce homopolyethylene, also called polyethylene. It should be noted, however, that some of the catalysts of this invention homopolymerize ethylene or propylene to non-traditional “polyethylene” and “polypropylene” structures, respectively. Likewise, “copolymerization” would produce polymers with more than one monomer type. For example, ethylene copolymers include polymers of ethylene with α-olefins, cyclic olefins and diolefins, vinylaromatic olefins, α-olefinic diolefins, substituted α-olefins, and/or acetylenically unsaturated monomers. Non-limiting examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane. Non-limiting examples of cyclic olefins and diolefins include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane. Non-limiting examples of vinylaromatic olefins include styrene, para-methylstyrene, para-t-butylstyrene, vinylnaphthylene, vinyltoluene, and divinylbenzene. Non-limiting examples of α-olefinic dienes include 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, 1,11-dodecene, 1,13-tetradecene and 9-methyl-1,9-decadiene. Substituted α-olefins (also called functional group containing α-olefins) include those containing at least one non-carbon Group 13 to 17 atom bound to a carbon atom of the substituted α-olefin where such substitution if silicon may be adjacent to the double bond or terminal to the double bond, or anywhere in between, and where inclusion of non-carbon and -silicon atoms such as for example B, O, S, Se, Te, N, P, Ge, Sn, Pb, As, F, Cl, Br, or I, are contemplated, where such non-carbon or -silicon moieties are sufficiently far removed from the double bond so as not to interfere with the coordination polymerization reaction with the catalyst and so to retain the generally hydrocarbyl characteristic. By being sufficiently far removed from the double bond we intend that the number of carbon atoms, or the number of carbon and silicon atoms, separating the double bond and the non-carbon or -silicon moiety may be 6 or greater, e.g. 7, or 8, or 9, or 10, or 11, or 12, or 13, or 14 or more. The number of such carbon atoms, or carbon and silicon atoms, is counted from immediately adjacent to the double bond to immediately adjacent to the non-carbon or -silicon moiety. Examples include allyltrimethylsilane, divinylsilane, 8,8,8-trifluoro-1-octene, 8-methoxyoct-1-ene, 8-methylsulfanyloct-1-ene, 8-dimethylaminooct-1-ene, or combinations thereof. The use of functional group-containing α-olefins where the functional group is closer to the double bond is also within the scope of embodiments of the invention when such olefins may be incorporated in the same manner as are their α-olefin analogs. See, “Metallocene Catalysts and Borane Reagents in The Block/Graft Reactions of Polyolefins”, T. C. Chung, et al, Polym. Mater. Sci. Eng ., v. 73, p. 463 (1995), and the masked α-olefin monomers of U.S. Pat. No. 5,153,282. Such monomers permit the preparation of both functional-group containing copolymers capable of subsequent derivatization, and of functional macromers which may be used as graft and block type polymeric segments. All documents cited herein are incorporated by reference for purposes of all jurisdictions where such practice is allowed. Copolymerization can also incorporate α-olefinic macromonomers of up to 2000 mer units.
For purposes of this disclosure, the term oligomer refers to compositions having 2-75 mer units and the term polymer refers to compositions having 76 or more mer units. A mer is defined as a unit of an oligomer or polymer that originally corresponded to the olefin(s) used in the oligomerization or polymerization reaction. For example, the mer of polyethylene would be ethylene.
The terms “catalyst” and “catalyst compound” are defined to mean a compound capable of initiating catalysis. A catalyst compound may be used by itself to initiate catalysis or may be used in combination with an activator to initiate catalysis. When the catalyst compound is combined with an activator to initiate catalysis, the catalyst compound is often referred to as a pre-catalyst or catalyst precursor. The term “catalyst system” is defined to mean: 1) a catalyst precursor/activator pair, and or 2) a catalyst compound capable of initiating catalysis without an activator. When “catalyst system” is used to describe such a pair before activation, it means the unactivated catalyst (pre-catalyst) together with an activator and, optionally, a co-activator. When it is used to describe such a pair after activation, it means the activated catalyst and the activator or other charge-balancing moiety.
The catalyst compound may be neutral as in a pre-catalyst or a catalyst system not requiring an activator, or may be a charged species with a counter ion as in an activated catalyst system.
The terms “activator” and “cocatalyst” are used interchangeably herein. A scavenger is a compound that is typically added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments a co-activator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound, also referred to as an alkylated invention compound.
Noncoordinating anion (NCA) is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
A stoichiometric activator can be either neutral or ionic. The terms ionic activator, and stoichiometric ionic activator can be used interchangeably. Likewise, the terms neutral stoichiometric activator, and Lewis acid activator can be used interchangeably.
For purposes of this invention and the claims thereto, in describing a ligand, a terminal nitrogen atom, is a nitrogen atom that is indirectly bonded to only one other nitrogen atom. A central nitrogen atom is a nitrogen atom that is indirectly bonded to at least one other nitrogen atom and at least one oxygen atom. A terminal oxygen atom is an oxygen atom that is indirectly bonded to only the central nitrogen atom. An example is illustrated below:
DETAILED DESCRIPTION OF THE INVENTION
This invention further relates to transition metal compounds represented by formulae 1 to 5 and 7 to 11.
wherein
- each M is, independently, a group 4, 5, 6, 7, 8, 9, 10, or 11 transition metal, preferably a group 6, 7, 8, 9 or 10 transition metal, preferably chromium, manganese, iron, cobalt or nickel;
- N is nitrogen;
- O is oxygen;
- w is 1, 2, or 3;
- each X is, independently, a hydride, a halogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
- additionally, X may independently be selected from halogen, alkoxide, aryloxide, amide, phosphide, or other anionic ligand when Lewis-acid activators (such as methylalumoxane, aluminum alkyls, alkylaluminum alkoxides) or alkylaluminum halides (capable of donating a hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl X ligand to the transition metal component) are used, or when an ionic activator is capable of extracting X, provided that the resulting activated catalyst contains as least one M—H or M—C bond into which an olefin can insert;
- each R is, independently, hydrogen, or a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl;
- each R 1 and R 2 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl; or independently, may join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
- each R 3 , R 4 , R 5 , is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl; or independently, may join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
- each R 6 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl;
- each R 7 and R 9 is, independently, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl;
- each R 8 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl;
- each R 10 is, independently, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;
- each R 11 is, independently, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl or a group selected from NO 2 , sulfonate, halo, carboxyl, sulfonyl ester, a carboxylic ester group, or a perfluoroalkyl group; and
- each x is, independently, 1, 2, 3 or 4, preferably, x is 1;
- L′ is a neutral ligand bonded to M that may include molecules such as but not limited to acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine lithium chloride, ethylene, propylene, butene, octene, styrene, and the like; and
- m is 0, 1 or 2 and indicates the absence or presence of L′.
In a preferred embodiment the halocarbyls are fluorocarbyls and the substituted halocarbyls are substituted fluorocarbyls.
To illustrate members of the transition metal catalyst compounds useful in this invention, select any combination of the species listed in Table 1.
| R′, R 1 , R 2 , R 3 , R 4 , R 5 , | ||||
| R 6 , R 10 , R 11 | R 7 | X | M | L′ |
| hydrogen | propyl | chloride | vanadium | acetonitrile |
| methyl | butyl | bromide | chromium | diethyl ether |
| ethyl | pentyl | iodide | cobalt | tetrahydrofuran |
| propyl | hexyl | methyl | manganese | furan |
| butyl | heptyl | ethyl | iron | thiofuran |
| pentyl | octyl | propyl | nickel | chromane |
| hexyl | nonyl | butyl | copper | isochromane |
| heptyl | decyl | pentyl | niobium | thiochromane |
| octyl | undecyl | hexyl | tantalum | thioisochromane |
| nonyl | dodecyl | heptyl | molybdenum | quinuclidine |
| decyl | tridecyl | octyl | tungsten | benzofuran |
| undecyl | tetradecyl | nonyl | technetium | chromene |
| dodecyl | octacosyl | decyl | rhenium | isobenzofuran |
| tridecyl | nonacosyl | undecyl | ruthenium | isoquinoline |
| tetradecyl | triacontyl | dodecyl | osmium | oxazole |
| octacosyl | cyclohexyl | tridecyl | rhodium | phenanthridine |
| nonacosyl | cyclopentyl | tetradecyl | iridium | pyran |
| triacontyl | cycloheptyl | pentadecyl | palladium | pyridine |
| cyclohexyl | cyclooctyl | hexadecyl | platinum | quinoline |
| cyclopentyl | cyclodecyl | heptadecyl | silver | selenophene |
| cycloheptyl | cyclododecyl | octadecyl | gold | thiophene |
| cyclooctyl | naphthyl | nonadecyl | trimethylamine | |
| cyclodecyl | phenyl | eicosyl | triethylamine | |
| cyclododecyl | tolyl | heneicosyl | tributylamine | |
| naphthyl | benzyl | docosyl | dimethylaniline | |
| phenyl | phenethyl | tricosyl | trimethylphosphine | |
| tolyl | dimethylphenyl | tetracosyl | triphenylphosphine | |
| benzyl | trimethylphenyl | pentacosyl | ethylene | |
| phenethyl | methylphenyl | hexacosyl | propylene | |
| dimethylphenyl | ethylphenyl | heptacosyl | butene | |
| diethylphenyl | diethylphenyl | octacosyl | hexene | |
| anthracenyl | triethylphenyl | nonacosyl | octene | |
| adamantyl | propylphenyl | triacontyl | cyclohexene | |
| norbornyl | dipropylphenyl | hydride | vinylcyclohexene | |
| CF 3 | tripropylphenyl | phenyl | benzene | |
| NO 2 | Methylethylphenyl | benzyl | styrene | |
| t-butyl | dibutylphenyl | phenethyl | methylstyrene | |
| i-propyl | butylphenyl | tolyl | ||
| naphthyl | methoxy | |||
| fluoride | ethoxy | |||
| propoxy | ||||
| butoxy | ||||
| dimethylamido | ||||
| diethylamido | ||||
| methylethylamido | ||||
| phenoxy | ||||
| benzoxy | ||||
| allyl | ||||
A selection of catalyst precursors are detailed below. These are by way of an example only and are not intended to list every catalyst precursor that is within the scope of the invention:
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]iron dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]cobalt dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]nickel dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]copper dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]iron dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]cobalt dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]nickel dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]copper dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]iron dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]cobalt dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]nickel dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]copper dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]iron dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]cobalt dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]nickel dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]copper dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]iron dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]cobalt dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]nickel dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]copper dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]iron dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]cobalt dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]nickel dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]copper dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]iron dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]cobalt dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]nickel dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]copper dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]iron dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]cobalt dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy, 3′-t-butyl)-pyridine]nickel dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]copper dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]iron dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]cobalt dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]nickel dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]copper dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy)-pyridine]iron dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy)-pyridine]cobalt dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl((2′-hyd roxy)-pyridine]nickel dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy)-pyridine]copper dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]iron dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]cobalt dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]nickel dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]copper dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]iron dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]cobalt dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]nickel dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]copper dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]iron dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]cobalt dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]nickel dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]copper dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]iron dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]cobalt dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]nickel dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]copper dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]iron dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]cobalt dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]nickel dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]copper dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]iron dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]cobalt dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]nickel dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]copper dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]iron dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]cobalt dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]nickel dichloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]copper dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]iron dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]cobalt dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]nickel dichloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]copper dichloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]iron dichloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]cobalt dichloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]nickel dichloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]copper dichloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]iron dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]cobalt dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]nickel dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]copper dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]iron dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]cobalt dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]nickel dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy)-pyridine]copper dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]iron dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]cobalt dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]nickel dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy)-pyridine]copper dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]iron dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]cobalt dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]nickel dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]copper dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]iron dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]cobalt dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]nickel dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-phenyl)-pyridine]copper dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]iron dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]cobalt dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]nickel dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-phenyl)-pyridine]copper dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]iron dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]cobalt dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]nickel dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]copper dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]iron dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]cobalt dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy, 3′-t-butyl)-pyridine]nickel dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-meth oxy,3′-t-butyl)-pyridine]copper dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]iron dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]cobalt dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]nickel dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -methoxy,3′-t-butyl)-pyridine]copper dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy)-pyridine]iron dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy)-pyridine]cobalt dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl((2′-hyd roxy)-pyridine]nickel dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy)-pyridine]copper dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]iron dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]cobalt dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]nickel dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy)-pyridine]copper dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]iron dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]cobalt dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]nickel dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy)-pyridine]copper dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]iron dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]cobalt dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]nickel dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]copper dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]iron dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]cobalt dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]nickel dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-phenyl)-pyridine]copper dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]iron dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]cobalt dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]nickel dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-phenyl)-pyridine]copper dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]iron dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]cobalt dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]nickel dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]copper dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]iron dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]cobalt dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]nickel dibromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-hydr oxy,3′-t-butyl)-pyridine]copper dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]iron dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]cobalt dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]nickel dibromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -hydroxy,3′-t-butyl)-pyridine]copper dibromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]iron dibromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]cobalt dibromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]nickel dibromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-meth oxy)-pyridine]copper dibromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]iron chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]cobalt chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]nickel chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]copper chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]iron chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]cobalt chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]nickel chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]copper chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) ,3′-phenyl)-pyridine]iron chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]iron chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]iron chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]cobalt chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]nickel chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]copper chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel chloride
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]iron chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]cobalt chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]nickel chloride
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]copper chloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron chloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt chloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel chloride
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper chloride
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]iron bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]cobalt bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]nickel bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]copper bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]iron bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]cobalt bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]nickel bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]copper bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) ,3′-phenyl)-pyridine]iron bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]iron bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]iron bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]cobalt bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]nickel bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]copper bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel bromide
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]iron bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]cobalt bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]nickel bromide
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]copper bromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron bromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt bromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel bromide
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper bromide
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]iron methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]cobalt methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]nickel methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]copper methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]iron methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]cobalt methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]nickel methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]copper methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) ,3′-phenyl)-pyridine]iron methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]iron methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]iron methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]cobalt methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]nickel methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]copper methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel methyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]iron methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]cobalt methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]nickel methyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]copper methyl
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron methyl
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt methyl
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel methyl
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper methyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]iron benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]cobalt benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]nickel benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo) -pyridine]copper benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]iron benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]cobalt benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]nickel benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo)-pyridine]copper benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) ,3′-phenyl)-pyridine]iron benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]iron benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]cobalt benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]nickel benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-phenyl)-pyridine]copper benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]iron benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]cobalt benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]nickel benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-phenyl)-pyridine]copper benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel benzyl
- [2-acetyl(2,6-diisopropylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]iron benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]cobalt benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]nickel benzyl
- [2-acetyl(2,4,6-trimethylanil)-6-phenyl(2′-oxo, 3′-t-butyl)-pyridine]copper benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]iron benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]cobalt benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]nickel benzyl
- [2-acetyl(2,3,4,5,6-pentafluoroanil)-6-phenyl(2 -oxo,3′-t-butyl)-pyridine]copper benzyl
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]iron benzyl
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]cobalt benzyl
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]nickel benzyl, and
- [2-formyl(2,6-diisopropylanil)-6-phenyl(2′-oxo) -pyridine]copper benzyl.
This invention also further relates to transition metal compounds represented by formulae 11 and 12.
wherein
- M is a group 4, 5 or 6 transition metal, preferably a group 4 transition metal, preferably Ti, Zr or Hf;
- N is nitrogen;
- O is oxygen;
- each X is, independently, a hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted
- halocarbyl,
- w is 1, 2 or 3;
- additionally, X may independently be selected from halogen, alkoxide, aryloxide, amide, phosphide, or other anionic ligand when Lewis-acid activators (such as methylalumoxane, aluminum alkyls, alkylaluminum alkoxides) or alkylaluminum halides (capable of donating a hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl X ligand to the transition metal component) are used, or when an ionic activator is capable of extracting X, provided that the resulting activated catalyst contains as least one M—H or M—C bond into which an olefin can insert;
- each R 1 and R 2 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl; or independently, may join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
- each R 3 , R 4 , R 5 , is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl; or independently, may join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
- each R 6 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C 30 substituted halocarbyl, more preferably a C 1 to C 10 hydrocarbyl, a C 1 to C 10 substituted hydrocarbyl, a C 1 to C 10 halocarbyl, or a C 1 to C 10 substituted halocarbyl;
- each R 7 is, independently, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably, a C 1 to C 30 hydrocarbyl, a C 1 to C 30 substituted hydrocarbyl, a C 1 to C 30 halocarbyl, or a C 1 to C