WO2007059015A1 - Improved catalysts for alpha-olefin manufacture - Google Patents

Improved catalysts for alpha-olefin manufacture Download PDF

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WO2007059015A1
WO2007059015A1 PCT/US2006/043946 US2006043946W WO2007059015A1 WO 2007059015 A1 WO2007059015 A1 WO 2007059015A1 US 2006043946 W US2006043946 W US 2006043946W WO 2007059015 A1 WO2007059015 A1 WO 2007059015A1
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hydrogen
aryl
carbon group
substituted
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Alex Sergey Ionkin
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E.I. Du Pont De Nemours And Company
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53Nitrogen atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08Catalytic processes
    • C07C2/26Catalytic processes with hydrides or organic compounds
    • C07C2/32Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20Olefin oligomerisation or telomerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2531/02Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0244Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62Chromium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/842Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/845Cobalt
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22Organic complexes

Abstract

Iron, cobalt, chromium or vanadium complexes of 2,6- pyridjnedicarboxaldehydes diimines and 2,6-diacylpyridines diimines which are suitable for catalyzing the oligomerization of ethylene to α-olefins exhibit more prolonged catalytic activity and/or yields products with linear Schuiz-FIory distributions, if aryl groups attached to the imino carbon atom(s) are substituted with at least one m-aryl group.

Description

TITLE

IMPROVED CATALYSTS FOR α-OLEFIN MANUFACTURE FIELD OF THE INVENTION

Iron, cobalt, chromium or vanadium complexes of certain 2,6- pyridinecarboxaldehydediimines and 2,6-diacylpyridinediimines in which phenyl groups bound to imino nitrogen atoms are substituted in the meta position with aryl group(s) have longer catalytic lives, and other advantages, when used as catalysts to produce α-olefins by oligomerization of ethylene. TECHNICAL BACKGROUND α-Olefins are important items of commerce, hundreds of millions of kilograms being manufactured yearly. They are useful as monomers for (co)polymerizations and as chemical intermediates for the manufacture of many other materials, for example detergents and surfactants. α-Olefins are most commonly made by the oligomerization of ethylene. Many types of catalysts for this reaction are known, among them certain transition metal complexes of diimines of 2,6-pyridinecarboxaldehydes and 2,6- diacylpyridines and related compounds, see for instance US6103946, US6534691, US6555723, US6683187 and US 6710006, and WO04/026795, all of which are also incorporated by reference.

As with any catalyst system one is normally concerned about the length of time the catalyst remains active and/or retains a good percentage of its activity over a prolonged period. The diimine complex catalysts mentioned above often have good activity but this diminishes as the temperatures of the process is raised, particularly above about 80-1000C. Therefore such catalysts with improved and/or prolonged activities, especially at higher temperatures, are desired. Another important attribute of such catalysts are the ability to yield a linear Schulz-Flory distribution of products, even when the ortho positions of the phenyl rings attached to the imino nitrogen's are symmetrical with respect to one another. Such symmetrical diimines are more easily synthesized from their respective anilines than such unsymmetrical diimines, the synthesis generally requiring at least one less step. Also often only one aniline need be used, as opposed to two different anilines being required for the unsymmetrical compounds. The use of unsymmetrically ortho substituted ligands to obtain linear Schulz-Flσry distributions is described in US 6710006.

SUMMARY OF THE INVENTION

This invention concerns a process for the oligomerization of ethylene to linear α-olefins (LAOs), comprising contacting, at a temperature of -2O0C to 2000C, ethylene and a Fe, Co, Cr or V complex of a ligand of the formula

Figure imgf000003_0001
wherein:

R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R1, R2 and R3 vicinal to one another taken together may form a ring;

R4 and R5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group provided that R1 and R4 and/or R3 and R5 taken together may form a ring; R6 and R7 are each independently phenyl or substituted phenyl having a first ring atom bound to the imino nitrogen, provided that at least one of R6 and R7 is substituted in at least one meta position with an aryl or substituted aryl group.

This invention also includes the ligands (I), and their Fe, Co, Cr or V complexes. BRIEF DESCRIPTION OF THE FIGURE

Figure 1 shows the Schulz-Flory distributions of α-olefins obtained from iron complexes 1 and 22.

DETAILS OF THE INVENTION Herein certain terms are used, and many of them are defined below.

A "hydrocarbyl group" is a univalent group containing only carbon and hydrogen. As examples of hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred that hydrocarbyl groups (and alkyl groups) herein contain 1 to about 30 carbon atoms.

By "substituted hydrocarbyl" herein is meant a hydrocarbyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected (e.g., an inert functional group, see below). The substituent groups also do not substantially detrimentally interfere with the polymerization process or operation of the polymerization catalyst system. If not otherwise stated, it is preferred that (substituted) hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted" are rings containing one or more heteroatoms, such as nitrogen, oxygen and/or sulfur, and the free valence of the substituted hydrocarbyl may be to the heteroatom. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl.

By "(inert) functional group" herein is meant a group, other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially deleteriously interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), and ether such as -OR50 wherein R50 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near a transition metal atom, the functional group alone should not coordinate to the metal atom more strongly than the groups in those compounds that are shown as coordinating to the metal atom, which is they should not displace the desired coordinating group. By a "cocatalyst" or a "catalyst activator" is meant one or more compounds that react with a transition metal compound to form an activated catalyst species. One such catalyst activator is an "alkylaluminum compound" which, herein, means a compound in which at least one alky! group is bound to an aluminum atom. Other groups such as, for example, alkoxide, hydride, an oxygen atom bridging two aluminum atoms and halogen may also be bound to aluminum atoms in the compound.

By a "linear α-olefin (LAO) product" is meant a composition predominantly comprising a compound or mixture of compounds of the formula H(CH2CH2)QCH=CH2 wherein q is an integer of 1 to about 18. In most cases, the LAO product of the present process will be a mixture of compounds having differing values of q of from 1 to 18, with a minor amount of compounds having q values of more than 18. Preferably less than 50 weight percent, and more preferably less than 20 weight percent, of the product will have q values over 18. The product may further contain small amounts (preferably less than 30 weight percent, more preferably less than 10 weight percent, and especially preferably less than 2 weight percent) of other types of compounds such as alkanes, branched alkenes, dienes and/or internal olefins. By a "primary carbon group" herein is meant a group of the formula

-CH2 — , wherein the free valence — is to any other atom, and the bond represented by the solid line is to a ring atom of a substituted aryl to which the primary carbon group is attached. Thus the free valence — may be bonded to a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a sulfur atom, etc. In other words, the free valence — may be to hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group. Examples of primary carbon groups include -CH3, -CH2CH(CH3)2, -CH2CI, -CH2C6H5, -OCH3 and -CH2OCH3.

By a "secondary carbon group" is meant the group

-CH

wherein the bond represented by the solid line is to a ring atom of a substituted aryl to which the secondary carbon group is attached, and both free bonds represented by the dashed lines are to an atom or atoms other than hydrogen and fluorine. These atoms or groups may be the same or different. In other words the free valences represented by the dashed lines may be hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples of secondary carbon groups include -CH(CH3)2, -CHCI2, -CH(C6Hs)2, cyclohexyl, -CH(CH3)OCH3, and -CH=CHCH3.

By a "tertiary carbon group" is meant a group of the formula

Figure imgf000006_0001
wherein the bond represented by the solid line is to a ring atom of a substituted aryl to which the tertiary carbon group is attached, and the three free bonds represented by the dashed lines are to an atom or atoms other than hydrogen and fluorine. In other words, the bonds represented by the dashed lines are to hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples of tetiary carbon groups include -C(CH3)3, -C(C6Hs)3, -CCI3, -C(CHs)2OCH3, -C≡CH, -C(CH3)2CH=CH2l aryl and substituted aryl such as phenyl, and 1-adamantyl.

By relatively noncoordinating (or weakly coordinating) anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al., Chem. Rev., vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Among such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X" including R9 3AIX", R9 2AICIX", R9AiCI2X", and "R9AIOX"", wherein R9 is alkyl. Other useful noncoordinating anions include BAF" {BAF = tetrakis[3,5- bis(trifluoromethyl)phenyl]borate}, SbF6 ", PF6 ", and BF4 ", trifluoromethanesulfonate

By a "monoanionic ligand" is meant a ligand with one negative charge.

By a "neutral ligand" is meant a ligand that is not charged. "Alkyl group" and "substituted alkyl group" have their usual meaning

(see above for substituted under substituted hydrocarbyl). Unless otherwise stated, alkyl groups and substituted alkyl groups preferably have 1 to about 30 carbon atoms.

By "aryl" is meant a monovalent aromatic group in which the free valence is to the carbon atom of an aromatic ring. An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups.

By "substituted aryl (phenyl)" is meant a monovalent aromatic (phenyl) group substituted as set forth in the above definition of "substituted hydrocarbyl", and also includes heteroarαmatic rings as substituted aryl groups. Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroatom in the ring, the free valence in the substituted aryl group can be to the heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon.

By "oligomerization conditions" herein is meant conditions for causing ethylene oligomerization with the catalysts described herein.

Such conditions may include temperature, pressure, oligomerization method such as liquid phase, continuous, batch, and the like. Also included may be cocatalysts that are needed and/or desirable. By a meta position is meant the usual meaning, meta to the first ring atom, i.e.

Figure imgf000008_0001
t wherein, as noted above, the nitrogen atom is connected to the first ring atom.

In (I) and its Fe, Co, Cr or V complexes the structures of R6 and R7 are particularly important in determining the Schulz-Flory constant of the mixtures of LAOs produced. This is a measure of the molecular weights of the olefins obtained, usually denoted as factor K, from the Schulz-Flory theory (see for instance B. Elvers, et a!., Ed. Ullmann's Encyclopedia of Industrial Chemistry, Vol. Al 3, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and 275-276). This is defined as:

K = n(Cn+2olefin)/n(Cn olefin) wherein n(Cn olefin) is the number of moles of olefin containing n carbon atoms, and n(Cn+2 olefin) is the number of moles of olefin containing n+2 carbon atoms, or in other words the next higher oligomer of

Cn olefin. From this can be determined the weight (mass) fractions of the various olefins in the resulting oligomeric reaction product mixture. The K factor is usually preferred to be in the range of about 0.6 to about 0.8 to make the α-olefins of the most commercial interest. It is also important to be able to vary this factor, so as to produce those olefins that are in demand at the moment.

In R6 and R7 it is further preferred that: in R6, a second ring atom adjacent to said first ring atom (ortho position) is bound to a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and further provided that in R6, when said second ring atom is bound to a halogen or a primary carbon group, none, one or two of the other ring atoms in R6 and R7 adjacent to said first ring atom are bound to a halogen or a primary carbon group, with the remainder of the ring atoms adjacent to said first ring atom being bound to a hydrogen atom; or in R6, when said second ring atom is bound to a secondary carbon group, none, one or two of the other ring atoms in R6 and R7 adjacent to said first ring atom are bound to a halogen, a primary carbon group or a secondary carbon group, with the remainder of the ring atoms adjacent to said first ring atom being bound to a hydrogen atom; or in R6, when said second ring atom is bound to a tertiary carbon group, none or one of the other ring atoms in R6 and R7 adjacent to said first ring atom are bound to a tertiary carbon group, with the remainder of the ring atoms adjacent to said first ring atom being bound to a hydrogen atom.

In addition to the substitution patterns described immediately above for the second ring atoms, at least one of the four meta positions in R6 and R7 combined must be substituted by an aryl or substituted aryl group.

In one preferred form R6 is

Figure imgf000009_0001
and R7 is

Figure imgf000009_0002
wherein these groups are substituted as described above.

(II) and (III) may be identical (so that substitution on the imino nitrogen atoms is "symmetric") or they may be different, including different in the (second) ortho positions and/or the meta positions (so that the substitution on the imino nitrogen atoms is "asymmetric"). Also (II) and (III) may be symmetric with respect to their ortho positions and unsymmetric with respect to their meta positions-, and vice versa.

In groups (II) and (III), with respect to the ortho positions, it is particularly preferred that if R8 is a primary carbon group or halogen, R13 is a primary carbon group or halogen, and R12 and R17 are hydrogen; or if R8 is a secondary carbon group, R13 is a primary carbon group, halogen or a secondary carbon group, more preferably a secondary carbon group, and R12 and R17 are hydrogen; or if R8 is a tertiary carbon group (more preferably a trihalo tertiary carbon group such as a trihalomethyl), and R12, R13 and R17 are hydrogen; or if R8 is a primary carbon group or halogen, R12 is a primary carbon group or halogen, and R13 and R17 are hydrogen; or if R8 is a secondary carbon group, R12 is a primary carbon group, halogen or a secondary carbon group, more preferably a secondary carbon group, and R13 and R17 are hydrogen.

In groups (II) and (II), with respect to the meta positions, it is particularly preferred that:

R9 is aryl or substituted aryl and R11, R14 and R16 are hydrogen; or R14 is aryl or substituted aryl and R9, R11 and R16 are hydrogen; or

R9 and R14 are each independently aryl or substituted aryl and R11 and R16 are hydrogen; or R9, R11, and R14 are each independently aryl or substituted aryl and

R16 is hydrogen; or

R9, R14, and R16 are each independently aryl or substituted aryl and R11 is hydrogen; or

R9, R11, R14 and R16 are each independently aryl or substituted aryl. In another preferred form of (II) and (II) with respect to the meta positions all of the aryl or substituted aryl groups are preferably the same.

In all preferred forms of (II) and (III), when they are not substituted as listed immediately above, it is preferred that those groups, R8 through R17, are hydrogen. It is also preferred that R1, R2 and R3 are hydrogen. It is preferred also that R4 and R5 are hydrogen or methyl, especially methyl.

It is to be understood that any preferred form of (II) and (III) with respect to the ortho positions, the meta positions, or any other positions in the ligand(l), may be combined to create a more preferred from of (I). Preferred aryl and substituted aryl groups are phenyl and substituted phenyl, and specific preferred groups are phenyl, tolyl (o-, m- or p-methyl), 3,5-bis(trifluoromethyl)phenyl, 5-methyl-2-thiophenyl, and p- fluorophenyl.

In the present complexes and their use as oligomerization catalysts, a preferred transition metal is iron. Preferably the oxidation state of the iron atom is +2.

Generally speaking the present complexes are effective oligomerization catalysts from about -200C to about 2000C, preferably about O0C to about 15O0C, and more preferably about 800C to about 15O0C. The pressure (if one or more monomers such as ethylene are gaseous) is not critical, atmospheric pressure to 70 MPa being a useful range. Any combination of temperature and pressure may be used. The particular combination of temperature and pressure chosen will reflect many factors, including oligomer yield, type of oligomerization process being used, the relative economics of various conditions, etc. A cocatalyst is often added which is an alkylating are hydriding agent. A preferred type of cocatalyst is an alkylaluminum compound, and preferred alkylaluminum compounds are methylaluminoxane, trimethylaluminum, and other trialkylaluminum compounds. Especially preferred alkylaluminum compounds are methylaluminoxane, trimethylaluminum. Useful forms of complexes of (II) include those of the following formulas (written as iron complexes, but analogous structures may be written for Co, Cr and V):

Figure imgf000012_0001
wherein:

R1, R2, R3, R4, R5, R6, and R7 are as defined above; each X is independently a monoanion; A is a π-allyl or π-benzyl group; L1 is a neutral monodentate ligand which may be displaced by said olefin or an open coordination site, and L2 is a monoanionic monodentate ligand which preferably can add to an olefin, or L1 and L2 taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may add to said olefin; and

Q is a relatively noncoordinating anion.

Preferably each X is independently halide or carboxylate, more preferably both of X are chloride or bromide. When A is present, in effect L1 and L2 taken together are A. (X) may be used as a starting material for forming an active polymerization complex. For example (X) may be reacted with:

(a) a first compound W, which is a neutral Lewis acid capable of abstracting X" and alkyl group or a hydride group from M to form WX", (WR40)" or WH", wherein R40 is alkyl, and which is also capable of transferring an alkyl group or a hydride to M, provided that WX" is a weakly coordinating anion; or

(b) a combination of second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of abstracting X", a hydride or an alkyl group from M to form a weakly coordinating anion. Thus W may be an alkylaluminum compound, while the second compound may be a dialkylzinc compound and the third compound may be a borane such as tris(pentafluorophenyl)borane. Such combinations and compounds for W are well known in the art, see for instance U.S. Patents 5,955,555 and 5,866,663, both of which are hereby included by reference.

In many instances compounds (Xl) or (XII), if added directly to an oligomerization process, may be active catalysts without the addition of any cocatalysts, or just the addition of a Lewis acid which may form a relatively noncoordinating anion by abstraction of A" or L2" from the complex. In (Xl) L2 may be an alkyl group, which is in fact an oligomer of the ethylene being oligomerized, while L'' may be an open coordination site or L1 is one of the olefins being polymerized. For example if ethylene is being oligomerized, L2 may be -(CH2CH2)ZD wherein z is a positive integer and D is an anion (which originally was L2) between which ethylene could insert between L2 and the Fe atom. The chemistry of such types of compounds is known; see for instance U.S. Patents 5,866,663 and 5,955,555, both of which are hereby included by reference.

The oligomerization process may be a batch, semibatch or continuous process, and a continuous process is preferred. Typically the process is carried out as a solution process, either with a separate solvent or using the LAOs as produced as the solvent. These types of processes are well known in the art. For example a solution process may be carried out in one or more continuous stirred tank reactors (CSTR), or a pipeline reactor. Such processes and conditions for the oligomerization are described in US6103946, US6534691 , US6555723, US6683187 and US 6710006, and WO04/026795, all of which were previously incorporated by reference.

All air-sensitive compounds were prepared and handled under a N2ZAr atmosphere using standard Schlenk and inert-atmosphere box techniques. Anhydrous solvents were used in the reactions. Solvents were distilled from drying agents or passed through columns under an argon or nitrogen atmosphere. Anhydrous iron(ll) chloride, 1-(6-acetyl-pyridin-2-yl)- ethanone, 3-bromo-2-methylphenylamine, 3,5-dibromo-4- methylphenylamine, 5-bromo-2-methylphenylamine, 4-fluorophenylboronic acid, 3,5-bis-trifluorornethylphenylboronic acid, 5-methyl-2-thiophene boronic acid, tris(dibenzylideneacetone) dipalladium (0), cesium carbonate, di-f-butylchlorophosphine, 2.0 M solution of benzylmagnesium chloride in THF, MMAO and n-butanol were purchased from Aldrich. Complex 1 was prepared according to US 5955555. In the Examples, THF is tetrahydrofuran. EXAMPLE 1 2,6-Bisd -(2-methyl-3-bromophenylimino)ethyl)pvricline (15)

Figure imgf000015_0001

15

1-(6-Acetylpyridin-2-y!)ethanone [18.87 g (0.116 mol)}, 45.3 g (0.243 mol) of 3-bromo-2-methylphenylamine, 300 ml of the toluene and a few crystals of para-tolue.nesulfonic acid were refluxed under a flow of nitrogen with a Dean-Stark trap for 3 d until the calculated amount of water was separated (4.16 ml). The solvent was removed by a rotary evaporator and the resultant reaction mixture was recrystaiiized from 50 ml of ethanol. The yield of 15 was 47.9 g (83%) as a pale yellow solid. 1H NMR (500 MHz, THF-D8, TMS ): δ 2.15 (s, 6 H, Me), 2.33 (s, 6 H, Me), 6.67 (m, 2H, Arom-H), 7.35 (m, 4H, Arom-H), 7.90 (t, 3JHH=7.8 HZ, 1H, Py-H), 8.50 (d, 3JHH=7.8 Hz, 2H, Py-H). 13C NMR (500 MHz, THF-D8, (selected signals)): δ 168.0 (C=N). Anal. Calculated for C23H2IBr2N3 (MoI. Wt.: 499.24): C, 55.33; H, 4.24; N, 8.42. Found: C, 55.40; H, 4.42; N, 8.46.

EXAMPLE 2 2,6-Bisd -(2-methyl-3-(4-fluoropheπyl)phenylimino)ethvπpyridine (18)

Figure imgf000015_0002

4-Fluorophenylboronic acid [4.71 g (0.0337 mol)], 5.60 g (0.0112 mol) of 15, 10.97 g (0.0337 mol) of cesium carbonate, 0.77 g (0.00084 mol) of tris(dibenzylideneacetone) dipalladium (0), 0.35 g (0.0016 mol) of di-f~butyl(2,2-dimethylpropyl)phosphane and 50 ml of dioxane were stirred at room temperature for 24 h. The reaction mixture was filtered and the solvent was removed under vacuum. The resulting mixture was purified by recrystallization from 20 ml of ethanol. Yield of 18 was 3.74 g (63%) as a light yellow solid. 1H NMR (500 MHz, CD2CI2, TMS ): δ 1.95 (s, 6 H, Me), 2.40 (s, 6 H, Me), 6.63 (m, 2H, Arom-H), 7.40 (m, 14H1 Arom-H), 7.91 (t, 3JHH=7.8 HZ, 1H, Py-H), 8.40 (d, 3JHH=7.8 HZ, 2H1 Py-H). 13C NMR (500 MHz, CD2CI2, (selected signals)): δ 168.1 (C=N). 19F NMR (CD2CI2) - 117.32 (s, 2F). Anal. Calcd. for C35H29F2N3 (MoI. Wt: 529.62): C, 79.37; H, 5.52; N, 7.93. Found: C, 79.52; H, 5.69; N, 8.14.

EXAMPLE 3

2,5-Bis(1-(2-methy!-3-(3,5- bis(trifluoromethyl)phenyl)phenyliminotethvQpyridine (19)

Figure imgf000016_0001

3,5~Bis(trifluoromethyl)phenyIboronic acid, 16, [7.44 g (0.0289 mol)}, 4.80 g (0.0096 mol) of 15, 9.40 g (0.0289 mo!) of cesium carbonate, 0.66 g (0.00072 mol) of tris(dibenzylideneacetone) dipalladium (0), 0.38 g (0.0018 mol) of di-f-butyl(2,2-dimethylpropyl)phosphane and 50 ml of dioxane were stirred at room temperature for 24 h. The reaction mixture was filtered and the solvent was removed under vacuum. The resulting mixture was purified by recrystallization from 20 ml of ethanol. Yield of 19 was 5.14 g (76%) as a slight yellow solid. 1H NMR (500 MHz, CD2CI2, TMS ): δ 2.05 (s, 6 H, Me), 2.41 (s, 6 H, Me), 6.68 (m, 2H, Arom-H), 7.05 (m, 2H, Arom-H), 7.30 (m, 2H, Arom-H), 7.95 (m, 7H1 Arom-H and Py-H), 8.45 (d, 3JHH=7.8 HZ, 2H, Py-H). 13C NMR (500 MHz, CD2CI2, (selected signals)): δ 167.7 (C=N). 19F NMR (CD2CI2) - 63.54 (s, 12F). Anal. Calcd. for C39H27Fi2N3 (MoI. Wt: 765.63): C, 61.18; H, 3.55; N, 5.49. Found: C, 61.36; H, 3.70; N, 5.52. The structure was proven by X-ray analysis. EXAMPLE 4

2,6-Bis(1-(2-methyl-3-(3-methylthiophene-2-yl)- phenyl)ρhenylimino)ethyl)pyridine (20)

Figure imgf000017_0001

5-Methyl-2-thiσphene boronic acid [10.0 g (0.0704 mol)], 8.79 g (0.0176 mo!) of 15, 22.95 g (0.0704 mol) of cesium carbonate, 1.62 g (0.00177 mol) of tris(dibenzylideneacetone) dipalladium (0), 0.91 g (0.0042 mol) of di-f-butyl(2,2-dimethylpropyl)phosphane and 50 ml of dioxane were stirred at room temperature for 24 h. The reaction mixture was filtered and the solvent was removed under vacuum. The resulting mixture was purified by recrystallization from 20 ml of ethanol. Yield of 20 was 3.26 g (35%) as a light yellow solid. 1H NMR (500 MHz, C6D6, TMS): δ 2.12 (s, 6 H, Me), 2.32 (s, 6 H, Me), 2.39 (s, 6 H, Me), 6.50 (s, 2H, Arom-H), 6.70 (m, 2H, Arom-H), 7.20 (m, 7H, Arom-H), 8.49 (d, 3JHH=7.8 Hz, 2H, Py-H). 13C NMR (500 MHz, C6D6, (selected signals)): δ 166.6 (C=N). Anal. Calcd. for C33H3-IN3S2 (MoI. Wt: 533.75): C, 74.26; H, 5.85; N, 7.87. Found: C, 74.29; H, 5.91; N, 7.95.

EXAMPLE 5

2,6-Bisd-('2-methyl-3-(4-fluorophenyl)phenylimino)ethyl)pyridine iron (II) chloride (21)

Figure imgf000017_0002

21

Anhydrous iron(ll) chloride [0.43 g (0.0034 mol)] was dissolved in 40 ml warm n-butanol. Then, 2.0 g (0.0038 mol) of 18 was added in one portion in the reaction mixture. The mixture was kept at 40°C for 1 h and then was cooled to ambient temperature. The resultant blue precipitate was filtered off and washed twice by 20 ml of pentane and dried at 133 Pa pressure. Yield of 21 was 3.83 g (87%). Anal. Calculated for C35H29CI2F2FeN3 (MoI. Wt: 656.37): C, 64.05; H, 4.45; N, 6.40. Found: C, 64.23; H, 4.61 ; N, 6.48. Direct probe MSr Exact Mass for C35H29CI2F2FeN3: 655.11. Found: 655.11.

EXAMPLE 6

2,6-Bisf 1 -(2-methyl-3-(3,5- bis(trifluoromethyl)phenyl)phenylimino)ethyl)pyridine iron (II) chloride (22)

Figure imgf000018_0001

Anhydrous iron(ll) chloride [0.50 g (0.0039 mol)] was dissolved in 40 ml warm n-butanol. Then, 3.0 g of 19 was added in one portion into the solution. The mixture was kept at 4O0C for 1 h and then was cooled to ambient temperature. The resultant blue precipitate was filtered off and washed twice by 20 ml of pentane and dried at 133 Pa pressure. Yield of 22 was 3.83 g (87%). Anal. Calculated for C39H27CI2Fi2FeN3 (MoI. Wt: 892.38): C, 52.49; H, 3.05; N, 4.71. Found: C, 52.57; H, 3.21 ; N, 4.96. The structure was proven by X-ray analysis.

EXAMPLE 7

2,6-Bis(1-(2-methv)-3-(3-methylthiophene-2-yl)- phenyl)phenylimino)ethyl)pyridine iron (II) chloride (23)

Figure imgf000018_0002

23

20 [0.5 g (0.00094 mol)] was dissolved in 30 ml of THF, and then 0.11 g (0.00087 mol) of iron(ll) chloride was added in one portion. The resultant blue precipitate was filtered after 12 h of stirring, washed twice with 20 ml of pentane, and dried at 133 Pa pressure. Yield of 23 was 1.34 g (84%). Anal. Calculated for C33H3ICI2FeN3S2 (MoI. Wt: 660.50): C, 60.01 ; H, 4.73; N, 6.36. Found: C, 60.25; H, 4.90; N, 6.39. Direct probe M& Exact Mass for C33H31CI2FeN3S2: Exact Mass: 659.07. Found Exact Mass: 659.07.

EXAMPLE 8

2.6-Bisf 1 -(2-methyl-3-(3,5- bis(trifluoromethyl)phenyl)phenylimino)ethyl)pyridine iron (III) chloride (24)

Figure imgf000019_0001

24

19 [1.O g (0.0013 mol)]was dissolved in 50 ml THF, and then 0.20 g (0.0012 mol) of anhydrous iron(lll) chloride was added in one portion. The mixture was stirred for 20 min at ambient temperature. The resultant orange precipitate was filtered of and washed twice with 20 ml of pentane and dried at 1 Pa pressure. Note - it is believed that this compound is slowly converted to the iron(ll) compound in THF by hydrogen abstraction. Yield of 24 was 0.88 g (73%). Anal. Calculated for C39H27CI3F12FeN3 (MoI. Wt: 927.84): C, 50.48; H, 2.93; N, 4.53. Found: C, 50.59; H, 3.20; N, 4.57. Direct probe MS: Exact Mass for C39H27CI3F12FeN3: 926.04. Found: 926.04.

EXAMPLE 9 2.6-Bis(1 -(2-methyl-5-bromo-phenylimino)ethyl)pyridine (26)

Figure imgf000019_0002

26

1-(6-Acetyl-pyridin-2-yl)ethanone [8.33 g (0.051 mol)], 20.0 g (0.107 mol) of 5-bromo-2-methyl-pheny!amine and 200 ml of dry toluene with a few crystals of para-toluenesulfonic acid were refluxed under the flow of the nitrogen using a Dean-Stark trap for 3 d until the calculated amount of the water was separated (1.84 mi). The solvent was removed in a rotary evaporator and the resultant reaction mixture was recrystallized from 50 ml of ethanol. The yield of 26 was 19.88 g (78%) as a pale yellow solid. 1H NMR (500 MHz, C6D6, TMS): δ 1.90 (s, 6 H, Me), 2.12 (s, 6 H, Me), 6.50 (m, 2H, Arom-H), 7.20 (m, 4H, Arom-H), 7.30 (t, 3JHH=7.8 HZ, 1 H1 Py-H), 8.40 (d, 3JHH=7.8 HZ, 2H, Py-H). 13C NMR (500 MHz, C6D6, (selected signals)): δ 167.4 (C=N). Anal. Calculated for C23H2IBr2N3 (MoI. Wi: 499.24): C, 55.33; H, 4.24; N, 8.42. Found: C, 55.48; H, 4.45; N, 8.53.

EXAMPLE 10 Benzyl-di-f-butylphosphane (28)

Di-f-butylchlorophosphine [75.0 g (0.415 mol) and 0.5 mole of a 2.0 M solution of benzylmagnesium chloride in THF (200 ml) were refluxed under argon for 2 days. The reaction mixture was allowed to cool off to RT and an aqueous solution of ammonium chloride was added slowly. The organic phase was separated, and dried with magnesium sulfate. After removal of the solvent, the product was purified by distillation in vacuum. The yield of 28 was 94.3 g (96%) with b.p. 56-59°C/13 Pa. 31P NMR (CDCI3) + 36.63 ppm. 1H NMR (CDCI3) 1.18 (s, 9H, Me3C), 1.20 (s, 9H, Me3C), 2.90 (d, 2JPH= 2.92 Hz, P-CH2-Ph), 7.1- 7.6 (m, 5H, aromatic protons). Anal. Calcd. for C15H25P (MoI. Wt: 236.33): C, 76.23; H, 10.66; P, 13.11. Found: C, 76.15; H, 10.58; P, 12.87.

EXAMPLE 11

2,6-Bis(1-(5-(3,5-bis(trifluoromethylbhenvn-6-methyl phenylimino)ethyl)pyridine (27)

Figure imgf000020_0001

3,5-Bis-trifluoromethylphenylboronic acid [10.3 g (0.04 mol)], 5.0 g (0.01 mol) of 26, 12.64 g (0.0388 mol) of cesium carbonate, 0.71 g (0.00078 mol) of tris(dibenzylideneacetone) dipalladium (0), 0.55 g (0.00233 mol) of 28, and 50 ml of dioxane were stirred at room temperature for 24 h. The reaction mixture was filtered and the solvent was removed under vacuum. The resulting mixture was purified by recrystallization from 20 ml of ethanol. Yield of 27 was 4.45 g (58%) as a light yellow solid. 1H NMR (500 MHz, C6D6, TMS): δ 2.10 (s, 6 H, Me), 2.32 (s, 6 H, Me), 6.80 (s, 2H, Arom-H), 6.85 (m, 2H, Arom-H), 7.11 (m, 2H, Arom-H), 7.30 (m, 2H, Arom-H), 7.40 (t, 3JHH=7.8 HZ, 1 H, Py-H), 7.60 (s, 2H, Arom-H), 7.80 (s, 4H, Arom-H), 8.50 (d, 3JHH=7.8 HZ, 2H, Py-H). 13C NMR (500 MHz, C6D6, (selected signals)): δ 167.3 (C=N). 19F NMR (C6D6) - 63.07 (s, 12F). Anal. Calcd. for C39H27F12N3 (MoI. Wt: 765.63): C, 61.18; H, 3.55; N, 5.49. Found: C, 61.19; H, 3.50; N, 5.57.

EXAMPLE 12

2,6-Bis(1-(5-(3,5-bis(trifluoromethyl)phenyl)-6-methyl phenylimino)ethvOpyridine iron (II) chloride (30)

Figure imgf000021_0001

30

27 [0.9 g (0.00118 mol)] was dissolved in 30 ml of THF, and then 0.13 g (0.001 mol) of anhydrous iron(ll) chloride was added in one portion. The resultant blue precipitate was filtered after 12 h of stirring, washed twice by 20 ml of pentane, and dried at 133 Pa pressure. Yield of 30 was 0.95 g (83%). Anal. Calculated for C39H27CI2Fi2FeN3 (MoI. Wt.: 892.38): C, 52.49; H, 3.05; N, 4.71. Found: C, 52.54; H, 3.14; N, 4.78. The structure was proven by X-ray analysis.

EXAMPLE 13

1-(6-ri-(4-Bromo-2,6-dirr!ethyl-phenylirnino)-ethyll-pyridin-2-yl)-ethanone

(31)

Figure imgf000022_0001

1-(6-Acetyl-pyridin-2-yl)-ethanone [22.5 g (0.138 mol)], 25.0 g

(0.125) of 4-bromo-2,6-dimethylpheny!amine and 300 ml of n-propanol with a few crystals of p-toulenesulfonic acid were stirred at room temperature for 36 h in a 500 ml flask under a flow of the nitrogen. The resultant yellow precipitate was filtered and washed with 20 ml of methanol. It was then dried at 133 Pa pressure overnight. The yield of 31 was 19.08 g (44%) as a yellow solid. 1H NMR (500 MHz, CD2CI2, TMS): δ 1.95 (s, 6 H, Me), 2.22 (s, 3 H, Me), 2.30 (s, 3 H, Me), 6.80 (s, 2H, Arom- H)1 7.95 (t, 3JHH=8.0 HZ1 1H, Py-H), 8.15 (d, 3JHH=8.0 HZ, 1H, Py-H), 8.40 (d, 3JHH=8.0 HZ, 1H, Py-H). 13C NMR (500 MHz, CD2CI2, TMS (selected signals)): δ 168.4 (C=N), 199.5 (C=O). Anal. Calculated for Ci7H17BrN2O (MoI. Wt.: 345.23): C, 59.14; H, 4.96; N, 8.11. Found: C, 59.18; H, 5.07; N, 8.15.

EXAMPLE 14

4-Bromo-2,6-dimethyl-phenyl)(1-f6-f1-(3,5-dibromo-4- methylphenylimino)ethyπpyridin-2-yl}-ethylidene)amine (32)

Figure imgf000022_0002

31 [5.0 g (0.0145 mol)], 4.45 g (0.016 mol) of 3,5-dibromo-4-methyl- phenylamine, 100 g of fresh molecular sieves and 100 ml of toluene were kept at 900C for 3 d under a flow of nitrogen. The solvent was removed by a rotary evaporator and the residue was recrystailized from 10 mf of ethanol. The yield of 32 was 5.75 g (67%) as a yellow solid. 1H NMR (500 MHz, CD2CI2, TMS): δ 1.60 (s, 6 H, Me), 2.10 (s, 3 H, Me), 2.15 (s, 3 H, Me), 2.45 (s, 3 H, Me), 6.97 (s, 2H, Arom-H), 7.15 (s, 2H, Arom-H), 7.40 (t, 3JHH=8.0 HZ, 1 H, Py-H), 8.20 (d, 3JHH=8.0 Hz, 1H, Py-H), 8.40 (d, 3JHH=8.0 Hz, 1H, Py-H). 13C NMR (500 MHz, CD2CI2, TMS (selected signals)): δ 168.5 (C=N), 164.4 (C=N). Anal. Calculated for C24H22Br3N3 (MoI. Wt: 592.16): C, 48.68; H, 3.74; N, 7.10. Found: C, 48.69; H, 3.82; N, 7.17. EXAMPLE 15

4-(3,5-Bis-trifluoromethylphenyl)-2,6-dimethyl-phenvπ(1-{6-ri-(3,5-(3,5- bis(trifluoromethyl)phenyl)-4-methylphenylimino)ethvnpyridin-2- vl}ethvlidene)amine (33)

Figure imgf000023_0001

3,5-Bis-trifluoromethylphenylboronic acid [9.92 g (0.0385 mol)], 3.80 g (0.0096 mol) of 32, 12.54 g (0.0385 mol) of cesium carbonate, 0.88 g (0.00096 mol) of tris(dibenzylideneacetone) dipalladium (0), 0.50 g (0.0023 mol) of dHf-butyl(2,2~dimethylpropyl)phosphane and 50 ml of dioxane were stirred at room temperature for 24 h. The reaction mixture was filtered and the solvent was removed under vacuum. The resulting mixture was purified by recrystallization from 20 ml of ethanol. Yield of 33 was 5.14 g (76%) as a light yellow solid. 1H NMR (500 MHz, CD2CI2, TMS ): δ 1.55 (s, 3 H, Me), 1.90 (s, 6 H, Me), 2.30 (s, 3 H, Me), 2.49 (s, 3 H, Me), 6.40 (s, 2H, Arom-H), 6.97 (s, 2H, Arom-H), 7.15 (s, 2H, Arom-H), 7.40 (t, 3JHH=8.0 HZ, 1H, Py-H), 7.60 (s, 4H, Arom-H), 8.20 (d, 3JHH=8.0 HZ, 1 H, Py-H), 8.40 (d, 3JHH=8.0 HZ, 1 H, Py-H). 13C NMR (500 MHz, CD2CI2, (selected signals)): δ 168.0 (C=N), 167.2 (C=N). 19F NMR (CD2CI2) δ - 62.96 (s, 12F), - 63.00 (s, 6F). Anal. Calcd. for C48H31F18N3 (MoI. Wt.: 991.75): C, 58.13; H, 3.15; IST, 4.24. Found: C1 58.25; H, 3.18; N, 4.30.

EXAMPLE 16

4-(3,5-Bis(trifiuoromethyl)phenyl)-2,6-dimethylphenyl)(1-(6-ri-(3,5-(3,5-bis- trifluoromethylphenyl)-4-methyl-phenylimino)ethvnpyridin-2- yl}ethylidene)amine iron (II) chloride (34)

Figure imgf000024_0001

34

33 [0.5 g (0.0005 mo!)] was dissolved in 20 ml of THF, and then 0.064 g (0.0005 mol) of anhydrous iron(II) chloride was added in one portion. The resultant blue precipitate was filtered off after 12 h of stirring, washed twice with 20 ml of pentane, and dried at 133 Pa pressure. Yield of 34 was 0.95 g (83%). Anal. Calculated for C48H3ICI2F18FeN3 (MoI. Wt: 1118.50): C, 51.54; H, 2.79; N, 3.76. Found: C, 51.57; H, 3.02; N, 3.94. The structure was proven by X-ray analysis.

EXAMPLES 17-30 and Comparative Example A

Oligomerization of Ethylene to g-Qlefins In these Examples complex 1 is

Figure imgf000024_0002

Oligomerization Procedure

The oligomerizations were done in a 1 -liter stainless steel Autoclave Engineering Zipperclave (Autoclave Engineers, Erie, PA 16509, USA). The iron complex and modified methylaluminoxane (modified methylalumoxane, 7 weight % solution in o-xylene, having some n-butyl groups in place of methyl groups, obtained from Akzo-Nobel Inc., Chicago, IL 60606 USA) cocatalyst were charged separately using stainless steel injection tubes. The steps for a typical oligomerization follow.

The injectors- were charged in a glove box. The cocatalyst was charged into the injector assembly along with a 10 ml chase of o-xylene. The complexes are prepared as suspensions in o-xylene (10mg/100 ml). A sample was withdrawn from a well-stirred suspension and was added to 10 ml of o-xylene. The injectors were attached to autoclave ports equipped with dip tubes. Nitrogen was sparged through the loose fittings at the attachment points prior to making them tight. The desired charge of o-xylene was then pressured into the autoclave. The agitator and heater were turned on, and when the desired temperature was reached, the cocatalyst was charged to the clave by blowing ethylene down through the cocatalyst injector. After a significant pressure rise was seen in the autoclave to indicate the cocatalyst and chase solvent have entered, the injector was isolated from the process using its valves. The pressure controller was then set to 34.5 kPa below the desired ethylene operating pressure and was put in the automatic mode to allow it to control the operation of the ethylene addition valve. When the pressure was 34.5 kPa below the desired operating pressure, the controller was put into manual mode and the valve was set to 0% output. When the batch temperature was stable and at the desired value, the catalyst was injected using enough nitrogen such that the pressure was boosted to the desired operating pressure. At the same time as the catalyst injection, the pressure controller was put in the automatic mode and the oligomerization started. The 34.5 kPa boost was obtained routinely by having a small reservoir between the nitrogen source and the catalyst injector. A valve was closed between the nitrogen source and the reservoir prior to injecting the catalyst so the same volume of nitrogen was used each time to inject the catalyst suspension. To stop the oligomerization, the pressure controller was put into manual, the ethylene valve was closed, and the reactor was cooled. The amount of metal complex used in the examples depended on the activity of that catalyst. This was done to minimize the exotherm but still enough to make enough σ-olefins for analysis.

Conditions and some results for the oligomerizations are shown in Table 1.

TABLE 1

Figure imgf000026_0001
a Conditions: solvent: o-xylene; pressure: 4.83 MPa(gauge); b Determined from GC, using extrapolated values for C-10 and C-12 olefins.

Figure 1 shows the Schulz-Flory distributions of α-olefins for oiigomerization using 1 (comparative Example A) and 22 (Example 21) as the complexes. It is surprising that 22, which is symmetrical with respect to ortho substitution of the phenyl rings attached to the imino nitrogen atoms, gives such a linear Schulz-Flory distribution, since it was previously believed the such symmetrical ligands led to nonlinear distributions as exemplified by 1 , see US 6710006. In Figure 1 the diamonds and upper line (on the left) represent the distribution obtained from 1, while the triangles and lower line (on the left) represent the distribution obtained from 22. The horizontal axis is the degree of polymerization (number of ethylene repeat units) minus 2, while the vertical axis is the natural logarithm of (the weight fraction of a certain degree of polymerization divided by that degree of polymerization). Table 2 gives ethylene flows (in L/min) with time (min) for selected runs at 12O0C, and is a measure of the activity and longevity of the catalyst (Note maximum measurable low rate is 12 L/min).

TABLE 2

Figure imgf000027_0001

Claims

1. A process for the oligomerization of ethylene to linear α- olefins, comprising contacting, at a temperature of -2O0C to 2000C, ethylene and an Fe, Co, Cr or V complex of a ligand of the formula
Figure imgf000028_0001
wherein:
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R1, R2 and R3 vicinal to one another taken together may form a ring;
R4 and R5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group provided that R1 and R4 and/or R3 and R5 taken together may form a ring;
R6 and R7 are each independently phenyl or substituted phenyl having a first ring atom bound to the imino nitrogen, provided that at least one of R6 and R7 is substituted in at least one meta position with an aryl or substituted aryl group.
2. The process as recited in claim 1 wherein R6 is
Figure imgf000028_0002
and R7 is
Figure imgf000029_0001
wherein: if R8 is a primary carbon group or halogen, R13 is a primary carbon group or halogen, and R12 and R17 are hydrogen; or
,5 if R8 is a secondary carbon group, R13 is a primary carbon group, haiogen or a secondary carbon group, more preferably a secondary carbon group, and R12 and R17 are hydrogen; or if R8 is a tertiary carbon group (more preferably a trihalo tertiary carbon group such as a trihalomethyl), and R12, R13 and R17 are 0 hydrogen; or if R8 is a primary carbon group or halogen, R12 is a primary carbon group or halogen, and R13 and R17 are hydrogen; or if R8 is a secondary carbon group, R12 is a primary carbon group, halogen or a secondary carbon group, more preferably a secondary 5 carbon group, and R13 and R17 are hydrogen.
3. The process as recited in any one of the preceding claims wherein R6 is
Figure imgf000029_0002
and R7 is
Figure imgf000029_0003
R9 is aryl or substituted aryl and R11, R14 and R16 are hydrogen; or R14 is aryl or substituted aryl and R9, R11 and R16 are hydrogen; or R3 and R'" are each independently aryl or substituted aryl and R11 and R16 are hydrogen; or
R9, R11, and R14 are each independently aryl or substituted aryl and R16 is hydrogen; or R9, R14, and R16 are each independently aryl or substituted aryl and
R11 Is hydrogen; or
R9, R11, R14 and R16 are each independently aryl or substituted aryl.
4. The process as recited in any one of the preceding claims wherein said temperature is about 8O0C to about 15O0C.
5. The process as recited in claim 1 which is batch, semi-batch or continuous.
6. A compound of the formula
Figure imgf000030_0001
wherein: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R1, R2 and R3 vicinal to one another taken together may form a ring; R4 and R5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group provided that R1 and R4 and/or R3 and R5 taken together may form a ring;
R6 and R7 are each independently phenyl or substituted phenyl having a first ring atom bound to the imino nitrogen, provided that at least one of R6 and R7 is substituted in at least one meta position with an aryl or substituted aryl group.
7. A compound which is a Fe, Co, Cr or V complex of a ligand of the formula
Figure imgf000031_0001
wherein:
R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R1, R2 and R3 vicinal to one another taken together may form a ring;
R4 and R5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group provided that R1 and R4 and/or R3 and R5 taken together may form a ring;
R6 and R7 are each independently phenyl or substituted phenyl having a first ring atom bound to the imino nitrogen, provided that at least one of R6 and R7 is substituted in at least one meta position with an aryl or substituted aryl group.
8. The compound as recited in claim 6 or 7 wherein R6 is
Figure imgf000031_0002
and R is
Figure imgf000031_0003
wherein: if R8 is a primary carbon group or halogen, R13 is a primary carbon group or halogen, and R12 and R17 are hydrogen; or it K" is a secondary carbon group, R13 is a primary carbon group, halogen or a secondary carbon group, more preferably a secondary carbon group, and R12 and R17 are hydrogen; or if R8 is a tertiary carbon group (more preferably a trihalo tertiary carbon group such" as a trihalomethyl), and R12, R13 and R17 are hydrogen; or if R8 is a primary carbon group or halogen, R12 is a primary carbon group or halogen, and R13 and R17 are hydrogen; or if R8 is a secondary carbon group, R12 is a primary carbon group, halogen or a secondary carbon group, more preferably a secondary carbon group, and R13 and R17 are hydrogen.
9. The compound as recited in claim 6, 7 or 8 wherein R6 is
Figure imgf000032_0001
and R7 is
Figure imgf000032_0002
R9 is aryl or substituted aryl and R11, R14 and R16 are hydrogen; or R14 is aryl or substituted aryl and R9, R11 and R16 are hydrogen; or R9 and R14 are each independently aryl or substituted aryl and R11 and R16 are hydrogen; or
R9, R11, and R14 are each independently aryl or substituted aryl and
R16 is hydrogen; or
R9, R14, and R16 are each independently aryl or substituted aryl and
R11 is hydrogen; or
R9, R11, R14 and R16 are each independently aryl or substituted aryl.
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