JP2001096164A - Ethylene trimerization catalyst and method for trimerizing ethylene using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently and highly selectively produce 1-hexene from ethylene. SOLUTION: An ethylene trimerization catalyst comprises a transition metal complex with a coordinated neutral multidentate ligand having a tripod type structure, represented by the formula LCrXn (L is a neutral multidentate ligand having a tripod type structure; X is one or more kinds selected from a group consisting of a halogen atom, an amide group, a sulphonyl group, and an alkoxy group; M is a transition metal complex among group 3-10 in the periodic table; and n is an integer equal to the oxidation number of the transition metal complex M), an alkyl metal compound, and radical anions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for trimerizing ethylene and a method for trimerizing ethylene using the catalyst. More specifically, linear low-density polyethylene (LLD)
The present invention relates to an ethylene trimerization catalyst for efficiently and highly selectively producing 1-hexene useful as a raw material comonomer for PE) from ethylene, and a method for ethylene trimerization using the catalyst.

[0002]

2. Description of the Related Art As a method for obtaining 1-hexene by trimerizing ethylene, for example, JP-A-62-265237 discloses a catalyst system comprising a chromium compound, polyhydrocarbyl aluminum oxide and a donor ligand. Have been. JP-A-6-239920 discloses a catalyst system comprising a chromium compound, a pyrrole-containing compound, a metal alkyl compound and a halide, and JP-A-8-59732 discloses a chromium compound, a metal alkyl compound and an acid amide or imide. A catalyst system comprising a compound is disclosed.

JP-A-6-298673 discloses a catalyst comprising an aluminoxane and a coordination complex of chromium salt with phosphine, arsine and / or stibine which is a polydentate ligand. Further, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. Hei 10-231317 discloses a catalyst comprising an aluminum compound and a chlorine complex or an alkyl complex of chromium coordinated with a specific nitrogen ligand.
A catalyst comprising a chromium complex coordinated with a cyclic polyamine or hydrotris (pyrazolyl) borate and an alkylaluminum compound is disclosed.

[0004]

However, Japanese Patent Application Laid-Open No. Sho 62-62
The method described in Japanese Patent Publication No. 265237 has a disadvantage that a large amount of polyethylene is by-produced simultaneously with 1-hexene. Also,
Since polyhydrocarbyl aluminum oxide (also referred to as aluminoxane), which is a component of the catalyst, is a polymer obtained by reacting alkyl aluminum with water, it is difficult to synthesize polyhydrocarbyl aluminum oxide having a certain quality. Therefore, there is a problem that a reaction with good reproducibility cannot be performed even in the ethylene trimerization reaction.

[0005] The method described in Japanese Patent Application Laid-Open No. 6-239920 has little polyethylene by-product and is considerably improved in this respect. However, the pyrrole-containing compound, which is a component of the catalyst, is a substance that is extremely unstable with respect to air, and is liable to be colored and deteriorated. Therefore, not only is it difficult to handle, but it is not sufficient as an industrial catalyst because it requires a treatment for removing coloring components or a new device after completion of the reaction. Also, Japanese Patent Application Laid-Open No. 8-597
In the method described in Japanese Patent Publication No. 32, it is necessary to use a specific imide compound, that is, maleimide, in order to obtain activity among acid amide or imide compounds which are constituent components of the catalyst. Since maleimide has low solubility, preparation of the catalyst is complicated, and maleimide is not only difficult to obtain but also expensive, and has a problem in terms of economy.

On the other hand, the method described in Japanese Patent Application Laid-Open No. 6-298673 has a problem that an aluminoxane which cannot be synthesized with good reproducibility must be used. Further, the method described in JP-A-10-7712 has a problem that the catalytic activity is low. Further, the method described in JP-A-10-231317 has the disadvantage that not only 1-hexene is produced more than polyethylene but also the selectivity of 1-hexene in the oligomer is low.

The present invention has been made in view of the above problems, and an object of the present invention is to produce 1-hexene useful as a raw material comonomer of LLDPE from ethylene efficiently and highly selectively, and to be easy to handle. An object of the present invention is to provide a catalyst for trimerizing ethylene and a method for trimerizing ethylene using the catalyst.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that transition metal complexes of the periodic table groups 3 to 10 in which specific polydentate ligands are coordinated. The ethylene trimerization catalyst, which comprises an alkyl metal compound and a radical anion, is stable and easy to handle, and when it is used, the ethylene trimerization reaction proceeds with high activity, and 1-hexene is formed with high selectivity. To complete the present invention.

That is, the present invention provides a catalyst for the trimerization of ethylene comprising a transition metal complex of Groups 3 to 10 of the periodic table coordinated with a neutral polydentate ligand having a tripod-type structure, an alkyl metal compound and a radical anion. It relates to a method for trimerizing ethylene using the same.

[0010]

Next, the present invention will be described in more detail.

In the present invention, as one component constituting the ethylene trimerization catalyst, the following general formula (1) LMX _n (1) (where L is a neutral polydentate ligand having a tripod-type structure) And X represents one or more selected from the group consisting of a halogen atom, an amide group, a sulfonyl group, and an alkoxy group, M represents a transition metal of Group 3 to 10 of the periodic table, and n represents the oxidation number of the transition metal M. The transition metal complex of Group 3 to 10 of the Periodic Table in which a neutral polydentate ligand having a tripod-type structure represented by the following formula is used.

The neutral polydentate ligand having a tripod-type structure to be coordinated with a transition metal complex of Groups 3 to 10 of the Periodic Table is not particularly limited. For example, the following general formula (2) )

[0013]

Embedded image

(Where j, k, and m are each independently 0
6 to an integer. D ¹ is each independently a divalent hydrocarbon group which may have a substituent, and L ¹ is each independently a substituent containing a Group 14, 15, 16 or 17 element of the periodic table. Represents a group. G ¹ represents carbon or silicon, R ¹ represents a hydrogen group, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ) Or the following general formula (3)

[0015]

Embedded image

(Where a, b, and c each independently represent 0
And u is an integer of 0 or 1. D ²
Are each independently a divalent hydrocarbon group which may have a substituent, L ² is each independently a group 14 of the periodic table,
It represents a substituent containing a Group 15, Group 16 or Group 17 element. G ² represents nitrogen or phosphorus, and R ² represents oxygen or sulfur. ) Are preferred.

In the above general formulas (2) and (3), D
There are no particular restrictions on the ¹ and D ^2, for example, an alkylene group, a cycloalkylene group, a phenylene group, a tolylene group and a xylylene group. Also,
Examples of the substituent include alkyl groups such as a methyl group and an ethyl group, and alkoxy groups such as a methoxy group and an ethoxy group.

In the general formulas (2) and (3), the substituents containing elements belonging to groups 14, 15, 16 or 17 of the periodic table represented by L ¹ and L ² are not particularly limited. For example, methoxy group, ethoxy group, propoxy group, alkoxy groups such as butoxy group, phenoxy group,
Aryloxy groups such as 2,6-dimethylphenoxy group, alkylthio groups such as methylthio group, ethylthio group, propylthio group and butylthio group, arylthio groups such as phenylthio group and tolylthio group, dimethylamino group,
Dialkylamino groups such as diethylamino group and bis (trimethylsilyl) amino group; diarylamino groups such as diphenylamino group; alkylarylamino groups such as methylphenyl group; dialkylphosphone groups such as dimethylphosphino group and diethylphosphino group. Examples thereof include diaryl phosphino groups such as a fino group, a diphenyl phosphino group and a ditolyl phosphino group, and alkylaryl phosphino groups such as a methyl phenyl phosphino group.

Further, furyl, benzofuryl, thienyl, benzothienyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, imidazolyl, benzimidazolyl, indazolyl, quinolyl, isoquinolyl, oxazolyl, thiazole And the like. Heterocyclic groups containing Group 14, 14, 15, 16 or 17 elements of the periodic table. Examples of the substituent on the ring of these heterocyclic groups include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a phenyl group and the like.

R ¹ in the general formula (2) is not particularly restricted but includes, for example, hydrogens, methyl, ethyl, propyl, butyl, benzyl, hydroxymethyl, cyanoethyl, allyl. And alkyl groups having 1 to 10 carbon atoms such as a trifluoropropyl group, and aryl groups having 6 to 10 carbon atoms such as a phenyl group, a p-methylphenyl group and a p-chlorophenyl group.

The neutral tridentate ligand having a tripod-type structure represented by the general formulas (2) and (3) is not particularly limited. Examples of the polydentate ligand having a substituent containing a Group 11 or Group 17 element include tris (methoxymethyl) methane, 1,1,1
-Tris (methoxymethyl) ethane, 1,1,1-tris (methoxymethyl) propane, 1,1,1-tris (methoxymethyl) butane, 1,1,1-tris (ethoxymethyl) ethane, 1,1 1,1-Tris (propoxymethyl) ethane, 1,1,1-tris (butoxymethyl) ethane, 1,1,1-tris (phenoxymethyl)
Oxygen-containing tridentate ligands such as ethane, 1,1,1-tris (methylthiomethyl) ethane, 1,1,1-tris (butylthiomethyl) ethane, 1,1,1-tris (phenylthiomethyl) ) Sulfur-containing tridentate ligands such as ethane,
1,1-tris (dimethylaminomethyl) ethane, 1,
Nitrogen-containing tridentate ligands such as 1,1-tris (diphenylaminomethyl) ethane, 1,1,1-tris (diphenylphosphinomethyl) ethane, 1,1,1-tris (dimethylphosphinomethyl) Phosphorus-containing tridentate ligands such as ethane and 1,1,1-tris (diethylphosphinomethyl) ethane are exemplified.

Further, the polydentate ligand having a heterocyclic group containing a Group 14, 15, 15, 16 or 17 element of the periodic table includes trifurylmethane and tris (5-methyl-2-
Furyl) methane, tris (5-ethyl-2-furyl) methane, tris (5-butyl-2-furyl) methane, 1,
Oxygen-containing tridentate ligands such as 1,1-trifurylethane, trifurylamine, trifurylphosphine, and trifurylphosphine oxide; sulfur-containing tridentate ligands such as tris (thienyl) methane; and tris (pyrazolyl) ) Methane, tris (3,5-dimethyl-1-pyrazolyl) methane, tris (3,5-diisopropyl-1-pyrazolyl) methane, tris (3,5-diphenyl-1-pyrazolyl) methane, 1,1,1 -Tris (3,5-dimethyl-1-pyrazolyl) ethane, 1,1,1-tris (3,5-dimethyl-1-pyrazolyl) propane, 1,1,1-tris (3,5-dimethyl-1) -Pyrazolyl) butane, tris (2-pyridyl) methane, tris (6-methyl-2-pyridyl) methane, tris (2-pyridyl) amine, tris (2-pyridyl) Sufin, tris (2-pyridyl) phosphine oxide, tris (2-pyridyl) hydroxymethyl methane, tris (1-imidazolyl) Motosan bidentate ligand such nitrogen such as methane and the like.

In the present invention, the halogen atom, amide group, sulfonyl group, and alkoxy group used for X in the above general formula (1) are not particularly limited. Examples of the halogen atom include a fluorine atom and a chlorine atom. , A bromine atom or an iodine atom. As the amide group,
For example, dimethylamide group, diethylamide group, di (n
-Propyl) amide group, di (iso-propyl) amide group, di (n-butyl) amide group, di (iso-butyl)
Amide group, di (sec-butyl) amide group, di (ter
Examples thereof include a (t-butyl) amide group, a dicyclohexylamide group, a di (n-octyl) amide group, a dibenzylamide group, a bis (trimethylsilyl) amide group, and a diphenylamide group. As the sulfonyl group, for example,
Examples thereof include a methanesulfonyl group, an ethanesulfonyl group, a benzenesulfonyl group, a toluenesulfonyl group, and a trifluoromethanesulfonyl group. Examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group,
iso-butoxy group, sec-butoxy group and ter
and a t-butoxy group.

The transition metals of Groups 3 to 10 of the periodic table used in the present invention are not particularly limited. For example, scandium, yttrium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, Rhenium, iron, ruthenium, cobalt, rhodium,
Nickel and the like can be exemplified. The valence of the transition metal is not particularly limited.

The periodic table 3-1 represented by the general formula (1)
Specific examples of the transition metal complex of Group 0 are not particularly limited.
But not for example, tris (methoxymethyl)
Methane scandium trichloride (III), 1,
1,1-tris (methoxymethyl) ethanescandium
Trichloride (III), 1,1,1-tris (eth
(Xymethyl) ethanescandium trichloride (II
I), 1,1,1-tris (butoxymethyl) ethanes
Candium trichloride (III), 1,1,1-to
Squirrel (phenoxymethyl) ethane scandium triclo
Ride (III), trifurylmethane scandium tri
Chloride (III), 1,1,1-tris (methylthio)
Omethyl) ethanescandium trichloride (II
I), 1,1,1-tris (dimethylaminomethyl)
Tanscandium trichloride (III), tris
(Pyrazolyl) methanescandium trichloride (I
II), tris (3,5-dimethyl-1-pyrazolyl)
Methane scandium trichloride (III), 1,
1,1-tris (3,5-dimethyl-1-pyrazolyl)
Ethanescandium trichloride (III), tris
(3,5-diisopropyl-1-pyrazolyl) methanes
Candium trichloride (III), tris (3,5
-Diphenyl-1-pyrazolyl) methanescandium
Lichloride (III), tris (2-pyridyl) meta
Scandium trichloride (III), tris (6
-Methyl-2-pyridyl) methanescandium triclo
Ride (III), tris (2-pyridyl) aminesca
Indium trichloride (III), tris (1-imi
Dazolyl) methane scandium trichloride (II
I), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethanescandium trichloride (III),
1,1,1-tris (diphenylphosphinomethyl)
Tanscandium trichloride (III), 1,1,
1-tris (diethylphosphinomethyl) ethanescan
Scandium complex such as didium trichloride (III)
Body, tris (methoxymethyl) methane titanium trichlora
Id (III), 1,1,1-tris (methoxymethyl
Le) ethane titanium trichloride (III), 1,1,
1-tris (ethoxymethyl) ethane titanium trichlora
Id (III), 1,1,1-tris (butoxymethi
Le) ethane titanium trichloride (III), 1,1,
1-tris (phenoxymethyl) ethane titanium trichloride
Ride (III), trifurylmethane titanium trichlora
Id (III), 1,1,1-tris (methylthiomethyl
Le) ethane titanium trichloride (III), 1,1,
1-tris (dimethylaminomethyl) ethane titanium tri
Chloride (III), tris (pyrazolyl) methane
Tantrichloride (III), tris (3,5-dimethyl
Tyl-1-pyrazolyl) methanetitanium trichloride
(III), 1,1,1-tris (3,5-dimethyl-
1-pyrazolyl) ethane titanium trichloride (II
I), tris (3,5-diisopropyl-1-pyrazoli)
Le) methane titanium trichloride (III), tris
(3,5-diphenyl-1-pyrazolyl) methane titanium
Trichloride (III), tris (2-pyridyl) meth
Tan titanium trichloride (III), tris (6-meth
Tyl-2-pyridyl) methanetitanium trichloride (I
II), tris (2-pyridyl) amine titanium trichloride
Ride (III), tris (1-imidazolyl) methane
Titanium trichloride (III), 1,1,1-tris
(Dimethylphosphinomethyl) ethane titanium trichlora
Id (III), 1,1,1-tris (diphenylphos
Finomethyl) ethane titanium trichloride (II
I), 1,1,1-tris (diethylphosphinomethyi)
Le) Titanium such as ethane titanium trichloride (III)
Complex, tris (methoxymethyl) methane vanadium tri
Chloride (III), 1,1,1-tris (methoxy
Methyl) ethanevanadium trichloride (III),
1,1,1-tris (ethoxymethyl) ethanevanadium
Mutrichloride (III), 1,1,1-tris
Toximethyl) ethanevanadium trichloride (II
I), 1,1,1-tris (phenoxymethyl) ethane
Vanadium trichloride (III), trifuryl meta
Nvanadium trichloride (III), 1,1,1-
Tris (methylthiomethyl) ethanevanadium triclo
Ride (III), 1,1,1-tris (dimethylamido
Nomethyl) ethanevanadium trichloride (II
I), tris (pyrazolyl) methane vanadium triclo
Ride (III), tris (3,5-dimethyl-1-pi
Lazolyl) methanevanadium trichloride (II
I), 1,1,1-tris (3,5-dimethyl-1-pi
Lazolyl) ethanevanadium trichloride (II
I), tris (3,5-diisopropyl-1-pyrazoli)
R) methanvanadium trichloride (III), tri
(3,5-diphenyl-1-pyrazolyl) methanebana
Diium trichloride (III), tris (2-pyridyl
R) methanvanadium trichloride (III), tri
(6-methyl-2-pyridyl) methane vanadium tri
Chloride (III), tris (2-pyridyl) amine
Vanadium trichloride (III), tris (1-a
Midazolyl) methanevanadium trichloride (II
I), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethanevanadium trichloride (III), 1,
1,1-tris (diphenylphosphinomethyl) ethane
Vanadium trichloride (III), 1,1,1-to
Lis (diethylphosphinomethyl) ethanevanadium
Vanadium complexes such as chloride (III), tris
(Methoxymethyl) methanechromium trichloride (II
I), 1,1,1-tris (methoxymethyl) ethane
Rom trichloride (III), 1,1,1-tris
(Ethoxymethyl) ethanechrome trichloride (II
I), 1,1,1-tris (butoxymethyl) ethane tank
Rom trichloride (III), 1,1,1-tris
(Phenoxymethyl) ethanechrome trichloride (I
II), trifurylmethanechromium trichloride (II
I), 1,1,1-tris (methylthiomethyl) ethane
Chromium trichloride (III), 1,1,1-tris
(Dimethylaminomethyl) ethanechrome trichloride
(III), tris (pyrazolyl) methanechrome trik
Chloride (III), tris (3,5-dimethyl-1-
Pyrazolyl) methanechrome trichloride (III),
1,1,1-tris (3,5-dimethyl-1-pyrazoli
Le) ethanechrome trichloride (III), tris
(3,5-diisopropyl-1-pyrazolyl) methanke
Lom trichloride (III), tris (3,5-diph
Enyl-1-pyrazolyl) methanechromium trichloride
(III), tris (2-pyridyl) methanechromium tri
Chloride (III), tris (6-methyl-2-pyri
Jill) methanechrome trichloride (III), tris
(2-pyridyl) amine chromium trichloride (II
I), tris (1-imidazolyl) methanechrome tric
Chloride (III), 1,1,1-tris
(Sphinomethyl) ethanechrome trichloride (II
I), 1,1,1-tris (diphenylphosphinomethyi)
Le) ethanechrome trichloride (III), 1,1,
1-tris (diethylphosphinomethyl) ethanechrome
Chromium complexes such as trichloride (III), tris (meth
Toximethyl) methanemanganese trichloride (II
I), 1,1,1-tris (methoxymethyl) ethanema
Ngan trichloride (III), 1,1,1-tris
(Ethoxymethyl) ethanemanganese trichloride (I
II), 1,1,1-tris (butoxymethyl) ethane
Manganese trichloride (III), 1,1,1-tri
(Phenoxymethyl) ethanemanganese trichloride
(III), trifurylmethane manganese trichloride
(III), 1,1,1-tris (methylthiomethyl)
Ethane manganese trichloride (III), 1,1,1
-Tris (dimethylaminomethyl) ethanemanganese tri
Chloride (III), tris (pyrazolyl) methane
Gantrichloride (III), tris (3,5-di
Methyl-1-pyrazolyl) methanemanganese trichlori
(III), 1,1,1-tris (3,5-dimethyl
-1-pyrazolyl) ethanemanganese trichloride (I
II), tris (3,5-diisopropyl-1-pyrazo)
Ril) methane manganese trichloride (III), tri
(3,5-diphenyl-1-pyrazolyl) methaneman
Gantrichloride (III), tris (2-pyridyl)
Le) methane manganese trichloride (III), tris
(6-Methyl-2-pyridyl) methanemanganese trichloride
Ride (III), tris (2-pyridyl) amine man
Gantrichloride (III), tris (1-imidazo
Ril) methanemanganese trichloride (III), 1,
1,1-tris (dimethylphosphinomethyl) ethanema
Ngan trichloride (III), 1,1,1-tris
(Diphenylphosphinomethyl) ethanemanganese tric
Chloride (III), 1,1,1-tris (diethyl
(Sphinomethyl) ethanemanganese trichloride (II
Manganese complex such as I), tris (methoxymethyl) meta
Iron trichloride (III), 1,1,1-tris
(Methoxymethyl) ethaneiron trichloride (II
I), 1,1,1-tris (ethoxymethyl) ethaneiron
Trichloride (III), 1,1,1-tris (but
(Xymethyl) ethaneiron trichloride (III), 1,
1,1-tris (phenoxymethyl) ethane iron triclo
Ride (III), trifurylmethane iron trichloride
(III), 1,1,1-tris (methylthiomethyl)
Ethane iron trichloride (III), 1,1,1-tri
(Dimethylaminomethyl) ethaneiron trichloride
(III), tris (pyrazolyl) methaneiron trichlora
Id (III), tris (3,5-dimethyl-1-pyra
Zolyl) methane iron trichloride (III), 1,1,
1-tris (3,5-dimethyl-1-pyrazolyl) ethane
Iron trichloride (III), tris (3,5-diyl
Sopropyl-1-pyrazolyl) methaneiron trichloride
(III), tris (3,5-diphenyl-1-pyrazo
Ril) methaneiron trichloride (III), tris (2
-Pyridyl) methane iron trichloride (III), tri
Tris (6-methyl-2-pyridyl) methaneiron trichloride
(III), tris (2-pyridyl) amine iron tric
Loride (III), tris (1-imidazolyl) meta
Iron trichloride (III), 1,1,1-tris
(Dimethylphosphinomethyl) ethaneiron trichloride
(III), 1,1,1-tris (diphenylphosphine
Nomethyl) ethaneiron trichloride (III), 1,
1,1-tris (diethylphosphinomethyl) ethaneiron
Iron complex such as trichloride (III), tris (Methoxy
(Cimethyl) methanecobalt trichloride (III),
1,1,1-tris (methoxymethyl) ethanecobalt
Trichloride (III), 1,1,1-tris (eth
Xymethyl) ethanecobalt trichloride (II
I), 1,1,1-tris (butoxymethyl) ethaneco
Baltic trichloride (III), 1,1,1-tris
(Phenoxymethyl) ethane cobalt trichloride
(III), trifurylmethane cobalt trichloride
(III), 1,1,1-tris (methylthiomethyl)
Ethane cobalt trichloride (III), 1,1,1
-Tris (dimethylaminomethyl) ethanecobalt tri
Chloride (III), tris (pyrazolyl) methaneco
Baltic trichloride (III), tris (3,5-di
Methyl-1-pyrazolyl) methanecobalt trichlori
(III), 1,1,1-tris (3,5-dimethyl
-1-pyrazolyl) ethanecobalt trichloride (I
II), tris (3,5-diisopropyl-1-pyrazo)
Ril) methanecobalt trichloride (III), tri
(3,5-diphenyl-1-pyrazolyl) methanecoba
Rutotrichloride (III), tris (2-pyridyl)
Le) methanecobalt trichloride (III), tris
(6-Methyl-2-pyridyl) methane cobalt trichloride
Ride (III), tris (2-pyridyl) amine kova
Lute trichloride (III), tris (1-imidazo
Ril) methanecobalt trichloride (III), 1,
1,1-tris (dimethylphosphinomethyl) ethaneco
Baltic trichloride (III), 1,1,1-tris
(Diphenylphosphinomethyl) ethanecobalt tric
Chloride (III), 1,1,1-tris (diethyl
(Sphinomethyl) ethanecobalt trichloride (II
I) and other cobalt complexes, tris (methoxymethyl) meta
Nickel trichloride (III), 1,1,1-to
Lis (methoxymethyl) ethane nickel trichloride
(III) 1,1,1-tris (ethoxymethyl) e
Tannickel trichloride (III), 1,1,1-
Tris (butoxymethyl) ethane nickel trichloride
(III), 1,1,1-tris (phenoxymethi
Le) ethane nickel trichloride (III), trif
Rylmethane nickel trichloride (III), 1,
1,1-tris (methylthiomethyl) ethane nickel oxide
Lichloride (III), 1,1,1-tris (dimethyl
Ruaminomethyl) ethane nickel trichloride (II
I), tris (pyrazolyl) methane nickel trichlora
Id (III), tris (3,5-dimethyl-1-pyra
Zolyl) methane nickel trichloride (III),
1,1,1-tris (3,5-dimethyl-1-pyrazoli
Le) ethane nickel trichloride (III), tris
(3,5-diisopropyl-1-pyrazolyl) methane
Heckell trichloride (III), tris (3,5-di
Phenyl-1-pyrazolyl) methane nickel trichlora
Id (III), tris (2-pyridyl) methanenicke
Rutrichloride (III), tris (6-methyl-2)
-Pyridyl) methane nickel trichloride (II
I), tris (2-pyridyl) amine nickel trichloride
Ride (III), tris (1-imidazolyl) methane
Nickel trichloride (III), 1,1,1-tri
(Dimethylphosphinomethyl) ethane nickel tric
Chloride (III), 1,1,1-tris (diphenyl
Phosphinomethyl) ethane nickel trichloride (I
II), 1,1,1-tris (diethylphosphinomethyi)
N) Nickel such as ethane nickel trichloride (III)
Kell complex, tris (pyrazolyl) methane yttrium thorium
Lichloride (III), tris (3,5-dimethyl-
1-pyrazolyl) methane yttrium trichloride
(III), 1,1,1-tris (3,5-dimethyl-
1-pyrazolyl) ethane yttrium trichloride
(III), tris (3,5-diisopropyl-1-pi
Lazolyl) methane yttrium trichloride (II
I), tris (3,5-diphenyl-1-pyrazolyl)
For example, methane yttrium trichloride (III)
Thorium complex, tris (pyrazolyl) methane molybdenum
Trichloride (III), tris (3,5-dimethyl
-1-pyrazolyl) methanemolybdenum trichloride
(III), 1,1,1-tris (3,5-dimethyl-
1-pyrazolyl) ethanemolybdenum trichloride (I
II), tris (3,5-diisopropyl-1-pyrazo)
Ril) methane molybdenum trichloride (III),
Lis (3,5-diphenyl-1-pyrazolyl) methanemo
Molybdenum complexes such as ribene trichloride (III)
Body, tris (pyrazolyl) methaneruthenium trichlora
Id (III), tris (3,5-dimethyl-1-pyra
Zolyl) methane ruthenium trichloride (III),
1,1,1-tris (3,5-dimethyl-1-pyrazoli
Le) ethane ruthenium trichloride (III), tri
(3,5-diisopropyl-1-pyrazolyl) methane
Ruthenium trichloride (III), tris (3,5
-Diphenyl-1-pyrazolyl) methaneruthenium tri
Ruthenium complexes such as chloride (III), tris (py
Lazolyl) methane rhodium trichloride (III),
Tris (3,5-dimethyl-1-pyrazolyl) methanlo
Didium trichloride (III), 1,1,1-tris
(3,5-dimethyl-1-pyrazolyl) ethane rhodium
Trichloride (III), Tris (3,5-diisoprop)
Ropyl-1-pyrazolyl) methane rhodium trichlori
De (III), tris (3,5-diphenyl-1-pyra
Such as zolyl) methane rhodium trichloride (III)
Halogenated transition coordinated by a neutral ligand such as rhodium complex
Metal complex, tris (methoxymethyl) methanescandiu
Mutrimethoxide (III), 1,1,1-tris (meth
Toximethyl) ethanescandium trimethoxide (I
II), 1,1,1-tris (ethoxymethyl) ethane
Scandium trimethoxide (III), 1,1,1-
Tris (butoxymethyl) ethanescandium trimet
Oxide (III), 1,1,1-tris (phenoxime
Chill) ethane scandium trimethoxide (III),
Trifurylmethane scandium trimethoxide (II
I), 1,1,1-tris (methylthiomethyl) ethane
Scandium trimethoxide (III), 1,1,1-
Tris (dimethylaminomethyl) ethanescandium
Limethoxide (III), tris (pyrazolyl) methane
Scandium trimethoxide (III), tris (3,
5-dimethyl-1-pyrazolyl) methane scandium
Limethoxide (III), 1,1,1-tris (3,5
-Dimethyl-1-pyrazolyl) ethanescandium tri
Methoxide (III), tris (3,5-diisopropyl
Ru-1-pyrazolyl) methanescandium trimethoxy
De (III), tris (3,5-diphenyl-1-pyra
Zolyl) methanescandium trimethoxide (II
I), tris (2-pyridyl) methanescandium tri
Methoxide (III), tris (6-methyl-2-pyri
Jill) methane scandium trimethoxide (III),
Tris (2-pyridyl) amine scandium trimethodine
Sid (III), tris (1-imidazolyl) methanes
Candium trimethoxide (III), 1,1,1-to
Lis (dimethylphosphinomethyl) ethanescandium
Trimethoxide (III), 1,1,1-tris (diff
Phenylphosphinomethyl) ethanescandium trimeth
Oxide (III), 1,1,1-tris (diethyl phos
Finomethyl) ethanescandium trimethoxide (I
II) and other scandium complexes, tris (methoxymethyl)
G) methane titanium trimethoxide (III), 1,1,
1-tris (methoxymethyl) ethane titanium trimetoki
Sid (III), 1,1,1-tris (ethoxymethy
Le) ethane titanium trimethoxide (III), 1,1,
1-tris (butoxymethyl) ethane titanium trimetoki
Sid (III), 1,1,1-tris (phenoxymethi
Le) ethane titanium trimethoxide (III), trifree
Methanetitanium trimethoxide (III), 1,1,1
-Tris (methylthiomethyl) ethane titanium trimetoki
Sid (III), 1,1,1-tris (dimethylamino
Methyl) ethane titanium trimethoxide (III), tri
Sub (pyrazolyl) methanetitanium trimethoxide (II
I), tris (3,5-dimethyl-1-pyrazolyl) me
Tin titanium trimethoxide (III), 1,1,1-to
Lis (3,5-dimethyl-1-pyrazolyl) ethanetita
Trimethoxide (III), tris (3,5-diiso
Propyl-1-pyrazolyl) methanetitaniumtrimethoxy
De (III), tris (3,5-diphenyl-1-pyra
Zolyl) methanetitanium trimethoxide (III), tri
(2-pyridyl) methanetitanium trimethoxide (II
I), tris (6-methyl-2-pyridyl) methane tita
Trimethoxide (III), tris (2-pyridyl)
Amine titanium trimethoxide (III), tris (1-
Imidazolyl) methanetitanium trimethoxide (II
I), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethane titanium trimethoxide (III), 1,1,
1-tris (diphenylphosphinomethyl) ethanetita
Trimethoxide (III), 1,1,1-tris (di
Ethylphosphinomethyl) ethane titanium trimethoxide
Titanium complex such as (III), tris (methoxymethyl)
Methane vanadium trimethoxide (III), 1,1,
1-tris (methoxymethyl) ethanevanadium trime
Toxide (III), 1,1,1-tris (ethoxyme
Chill) ethanevanadium trimethoxide (III),
1,1,1-tris (butoxymethyl) ethanevanadium
Mutrimethoxide (III), 1,1,1-tris
Enoxymethyl) ethanevanadium trimethoxide (I
II), trifurylmethane vanadium trimethoxide
(III), 1,1,1-tris (methylthiomethyl)
Ethanevanadium trimethoxide (III), 1,1,
1-tris (dimethylaminomethyl) ethanevanadium
Trimethoxide (III), tris (pyrazolyl) meta
Nvanadium trimethoxide (III), tris (3,
5-dimethyl-1-pyrazolyl) methanevanadium tri
Methoxide (III), 1,1,1-tris (3,5-
Dimethyl-1-pyrazolyl) ethanevanadium trimeth
Oxide (III), tris (3,5-diisopropyl-
1-pyrazolyl) methane vanadium trimethoxide (I
II), tris (3,5-diphenyl-1-pyrazoli
R) methane vanadium trimethoxide (III), tri
(2-pyridyl) methane vanadium trimethoxide
(III), tris (6-methyl-2-pyridyl) meta
Nvanadium trimethoxide (III), tris (2-
Pyridyl) amine vanadium trimethoxide (II
I), tris (1-imidazolyl) methanevanadium
Limethoxide (III), 1,1,1-tris (dimethyl
Ruphosphinomethyl) ethanevanadium trimethoxide
(III), 1,1,1-tris (diphenylphosphine
Nomethyl) ethanevanadium trimethoxide (II
I), 1,1,1-tris (diethylphosphinomethyi)
B) ethane vanadium trimethoxide (III)
Nadium complex, tris (methoxymethyl) methanechrome
Trimethoxide (III), 1,1,1-tris (meth
(Xymethyl) ethanechrome trimethoxide (III),
1,1,1-tris (ethoxymethyl) ethanechromate
Limethoxide (III), 1,1,1-tris (butoki)
(Cimethyl) ethanechrome trimethoxide (III),
1,1,1-tris (phenoxymethyl) ethanechrome
Trimethoxide (III), trifurylmethanechromate
Limethoxide (III), 1,1,1-tris (methyl
Thiomethyl) ethanechrome trimethoxide (III),
1,1,1-tris (dimethylaminomethyl) ethane
Lomtrimethoxide (III), tris (pyrazolyl)
Methanechrome trimethoxide (III), tris (3,
5-dimethyl-1-pyrazolyl) methanechromium trimethoate
Oxide (III), 1,1,1-tris (3,5-dimethyl
Tyl-1-pyrazolyl) ethanechrome trimethoxide
(III), tris (3,5-diisopropyl-1-pi
Lazolyl) methanechromium trimethoxide (III),
Squirrel (3,5-diphenyl-1-pyrazolyl) metanek
Lomtrimethoxide (III), tris (2-pyridi
G) methanechromium trimethoxide (III), tris
(6-Methyl-2-pyridyl) methanechrome trimethod
Sid (III), tris (2-pyridyl) amine chromium
Trimethoxide (III), tris (1-imidazoli)
G) methanechromium trimethoxide (III), 1,1,
1-tris (dimethylphosphinomethyl) ethanechrome
Trimethoxide (III), 1,1,1-tris (diff
Enylphosphinomethyl) ethanechrome trimethoxide
(III), 1,1,1-tris (diethylphosphino)
Methyl (meth) ethanechromium trimethoxide (III)
Lom complex, tris (methoxymethyl) methanemanganese
Limethoxide (III), 1,1,1-tris (Methoxy
(Cimethyl) ethanemanganese trimethoxide (III),
1,1,1-tris (ethoxymethyl) ethanemanganese
Trimethoxide (III), 1,1,1-tris (but
Xymethyl) ethanemanganese trimethoxide (II
I), 1,1,1-tris (phenoxymethyl) ethane
Manganese trimethoxide (III), trifurylmethane
Manganese trimethoxide (III), 1,1,1-tri
(Methylthiomethyl) ethanemanganese trimethoxide
(III), 1,1,1-tris (dimethylaminomethyl
Le) ethane manganese trimethoxide (III), tris
(Pyrazolyl) methanemanganese trimethoxide (II
I), tris (3,5-dimethyl-1-pyrazolyl) me
Tanmanganese trimethoxide (III), 1,1,1-
Tris (3,5-dimethyl-1-pyrazolyl) ethanema
Gantrimethoxide (III), tris (3,5-di
Isopropyl-1-pyrazolyl) methane manganese trime
Toxide (III), tris (3,5-diphenyl-1
-Pyrazolyl) methanemanganese trimethoxide (II
I), tris (2-pyridyl) methane manganese trimeth
Oxide (III), tris (6-methyl-2-pyridyl)
Le) methane manganese trimethoxide (III), tris
(2-pyridyl) amine manganese trimethoxide (II
I), tris (1-imidazolyl) methanemanganese tris
Methoxide (III), 1,1,1-tris (dimethyl
Phosphinomethyl) ethanemanganese trimethoxide (I
II), 1,1,1-tris (diphenylphosphinome
Chill) ethanemanganese trimethoxide (III), 1,
1,1-tris (diethylphosphinomethyl) ethanema
Manganese complexes such as gantrimethoxide (III);
Lis (methoxymethyl) methaneiron trimethoxide (II
I) 1,1,1-tris (methoxymethyl) ethaneiron
Trimethoxide (III), 1,1,1-tris (eth
(Xymethyl) ethaneiron trimethoxide (III), 1,
1,1-tris (butoxymethyl) ethane iron trimethod
Sid (III), 1,1,1-tris (phenoxymethi
Le) ethane iron trimethoxide (III), trifurylme
Iron trimethoxide (III), 1,1,1-tris
(Methylthiomethyl) ethaneiron trimethoxide (II
I), 1,1,1-tris (dimethylaminomethyl)
Iron trimethoxide (III), tris (pyrazoli
Le) methane iron trimethoxide (III), tris (3,
5-dimethyl-1-pyrazolyl) methaneiron trimethoxy
(III), 1,1,1-tris (3,5-dimethyl
-1-pyrazolyl) ethaneiron trimethoxide (II
I), tris (3,5-diisopropyl-1-pyrazoli)
Le) methane iron trimethoxide (III), tris (3,
5-diphenyl-1-pyrazolyl) methaneiron trimetoki
Sid (III), tris (2-pyridyl) methaneiron tri
Methoxide (III), tris (6-methyl-2-pyri
(Zyl) methaneiron trimethoxide (III), tris (2
-Pyridyl) amine iron trimethoxide (III), tri
(1-imidazolyl) methaneiron trimethoxide (II
I), 1,1,1-tris (dimethylphosphinomethyi)
L) ethane iron trimethoxide (III), 1,1,1-
Tris (diphenylphosphinomethyl) ethane iron trim
Toxide (III), 1,1,1-tris (diethyl
(Sphinomethyl) ethane iron trimethoxide (III), etc.
Iron complex, tris (methoxymethyl) methanecobalt
Limethoxide (III), 1,1,1-tris (Methoxy
(Cimethyl) ethanecobalt trimethoxide (III),
1,1,1-tris (ethoxymethyl) ethanecobalt
Trimethoxide (III), 1,1,1-tris (but
Xymethyl) ethanecobalt trimethoxide (II
I), 1,1,1-tris (phenoxymethyl) ethane
Cobalt trimethoxide (III), trifurylmethane
Cobalt trimethoxide (III), 1,1,1-tri
(Methylthiomethyl) ethane cobalt trimethoxide
(III), 1,1,1-tris (dimethylaminomethyl
Le) ethane cobalt trimethoxide (III), tris
(Pyrazolyl) methanecobalt trimethoxide (II
I), tris (3,5-dimethyl-1-pyrazolyl) me
Tancobalt trimethoxide (III), 1,1,1-
Tris (3,5-dimethyl-1-pyrazolyl) ethaneco
Bartotrimethoxide (III), Tris (3,5-di
Isopropyl-1-pyrazolyl) methanecobalt trime
Toxide (III), tris (3,5-diphenyl-1
-Pyrazolyl) methanecobalt trimethoxide (II
I), tris (2-pyridyl) methane cobalt trimeth
Oxide (III), tris (6-methyl-2-pyridyl)
Le) methanecobalt trimethoxide (III), tris
(2-pyridyl) amine cobalt trimethoxide (II
I), tris (1-imidazolyl) methanecobalt tri
Methoxide (III), 1,1,1-tris (dimethyl
Phosphinomethyl) ethanecobalt trimethoxide (I
II), 1,1,1-tris (diphenylphosphinome
Tyl) ethanecobalt trimethoxide (III), 1,
1,1-tris (diethylphosphinomethyl) ethaneco
Cobalt complexes such as bartotrimethoxide (III),
Lis (methoxymethyl) methane nickel trimethoxide
(III) 1,1,1-tris (methoxymethyl) d
Tannickel trimethoxide (III), 1,1,1-
Tris (ethoxymethyl) ethane nickel trimethoxy
(III), 1,1,1-tris (butoxymethyl)
Ethane nickel trimethoxide (III), 1,1,1
-Tris (phenoxymethyl) ethane nickel trimeth
Oxide (III), trifurylmethane nickel trimeth
Oxide (III), 1,1,1-tris (methylthiome
Chill) ethane nickel trimethoxide (III), 1,
1,1-tris (dimethylaminomethyl) ethane nickel
Rutrimethoxide (III), tris (pyrazolyl) meth
Tannickel trimethoxide (III), tris (3,
5-dimethyl-1-pyrazolyl) methane nickel trime
Toxide (III), 1,1,1-tris (3,5-di
Methyl-1-pyrazolyl) ethane nickel trimethoxy
(III), tris (3,5-diisopropyl-1-
Pyrazolyl) methane nickel trimethoxide (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methane nickel trimethoxide (III), tris (2
-Pyridyl) methane nickel trimethoxide (II
I), tris (6-methyl-2-pyridyl) methanenitride
Celtrimethoxide (III), tris (2-pyridyl)
B) amine nickel trimethoxide (III), tris
(1-imidazolyl) methane nickel trimethoxide
(III), 1,1,1-tris (dimethylphosphino
Methyl) ethane nickel trimethoxide (III),
1,1,1-tris (diphenylphosphinomethyl)
Tannickel trimethoxide (III), 1,1,1-
Tris (diethylphosphinomethyl) ethane nickel
Nickel complexes such as limethoxide (III)
Lazolyl) methane yttrium trimethoxide (II
I), tris (3,5-dimethyl-1-pyrazolyl) me
Tan yttrium trimethoxide (III), 1,1,
1-tris (3,5-dimethyl-1-pyrazolyl) ethane
Yttrium trimethoxide (III), tris
(3,5-diisopropyl-1-pyrazolyl) methanei
Thorium trimethoxide (III), tris (3,5
-Diphenyl-1-pyrazolyl) methane yttrium thorium
Yttrium complex such as limethoxide (III), tris
(Pyrazolyl) methane molybdenum trimethoxide (II
I), tris (3,5-dimethyl-1-pyrazolyl) me
Tammolybdenum trimethoxide (III), 1,1,1
-Tris (3,5-dimethyl-1-pyrazolyl) ethane
Molybdenum trimethoxide (III), tris (3,5
-Diisopropyl-1-pyrazolyl) methanemolybdenum
Trimethoxide (III), tris (3,5-diphenyl
Ru-1-pyrazolyl) methane molybdenum trimethoxide
Molybdenum complex such as (III), tris (pyrazolyl)
Methaneruthenium trimethoxide (III), tris
(3,5-dimethyl-1-pyrazolyl) methaneruthenium
Mutrimethoxide (III), 1,1,1-tris
(3,5-dimethyl-1-pyrazolyl) ethaneruthenium
Mutrimethoxide (III), tris (3,5-diiso
Propyl-1-pyrazolyl) methaneruthenium trimethate
Oxide (III), tris (3,5-diphenyl-1-
Pyrazolyl) methaneruthenium trimethoxide (II
Ruthenium complexes such as I), tris (pyrazolyl) methane
Rhodium trimethoxide (III), tris (3,5-
Dimethyl-1-pyrazolyl) methandrhodium trimetoki
Sid (III), 1,1,1-tris (3,5-dimethyl
Ru-1-pyrazolyl) ethane rhodium trimethoxide
(III), tris (3,5-diisopropyl-1-pi
Lazolyl) methandrhodium trimethoxide (III),
Tris (3,5-diphenyl-1-pyrazolyl) methane
Rhodium complexes such as rhodium trimethoxide (III)
Alkoxy transition metal complex coordinated with a neutral ligand
(Methoxymethyl) methane scandium trimethanes
Rufoxide (III), 1,1,1-tris (methoxy
Methyl) ethanescandium trimethanesulfoxide
(III) 1,1,1-tris (ethoxymethyl) e
Tanscandium trimethanesulfoxide (III),
1,1,1-tris (butoxymethyl) ethanescandi
Umtrimethanesulfoxide (III), 1,1,1-
Tris (phenoxymethyl) ethanescandium trim
Tansulfoxide (III), trifurylmethanescan
Dium trimethane sulfoxide (III), 1,1,1
-Tris (methylthiomethyl) ethanescandium tri
Methanesulfoxide (III), 1,1,1-tris
(Dimethylaminomethyl) ethanescandium trimeta
Sulfoxide (III), tris (pyrazolyl) meta
Scandium trimethanesulfoxide (III),
Lis (3,5-dimethyl-1-pyrazolyl) methaneska
Indium trimethanesulfoxide (III), 1,1,
1-tris (3,5-dimethyl-1-pyrazolyl) ethane
Scandium trimethanesulfoxide (III),
Lis (3,5-diisopropyl-1-pyrazolyl) meta
Scandium trimethanesulfoxide (III),
Lis (3,5-diphenyl-1-pyrazolyl) methanes
Candium trimethanesulfoxide (III), Tris
(2-pyridyl) methane scandium trimethanesulfo
Oxide (III), tris (6-methyl-2-pyridyl)
) Methane scandium trimethanesulfoxide (II)
I), tris (2-pyridyl) amine scandium tri
Methanesulfoxide (III), tris (1-imidazo
Ril) methane scandium trimethanesulfoxide (I
II), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethane scandium trimethanesulfoxide (II)
I), 1,1,1-tris (diphenylphosphinomethyi)
Le) ethane scandium trimethanesulfoxide (II)
I), 1,1,1-tris (diethylphosphinomethyi)
Le) ethane scandium trimethanesulfoxide (II)
Scandium complexes such as I), tris (methoxymethyl)
Methane titanium trimethane sulfoxide (III), 1,
1,1-tris (methoxymethyl) ethane titanium trim
Tansulfoxide (III), 1,1,1-tris (d
Toximethyl) ethane titanium trimethanesulfoxide
(III) 1,1,1-tris (butoxymethyl) d
Tantantrimethanesulfoxide (III), 1,
1,1-tris (phenoxymethyl) ethane titanium tri
Methanesulfoxide (III), trifurylmethane tita
Trimethanesulfoxide (III), 1,1,1-to
Lis (methylthiomethyl) ethane titanium trimethanesul
Foxide (III), 1,1,1-tris (dimethyla
Minomethyl) ethane titanium trimethanesulfoxide (I
II), tris (pyrazolyl) methane titanium trimethane
Sulfoxide (III), tris (3,5-dimethyl-
1-pyrazolyl) methanetitanium trimethanesulfoxide
(III), 1,1,1-tris (3,5-dimethyl-
1-pyrazolyl) ethane titanium trimethanesulfoxide
(III), tris (3,5-diisopropyl-1-pi
Lazolyl) methanetitanium trimethanesulfoxide (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methane titanium trimethane sulfoxide (III), tri
(2-pyridyl) methane titanium trimethane sulfoxy
(III), tris (6-methyl-2-pyridyl) meth
Tan titanium trimethanesulfoxide (III), tris
(2-pyridyl) amine titanium trimethanesulfoxide
(III), tris (1-imidazolyl) methane titanium
Trimethanesulfoxide (III), 1,1,1-tri
(Dimethylphosphinomethyl) ethane titanium trimeta
Sulfoxide (III), 1,1,1-tris (dif
Enylphosphinomethyl) ethanetitaniumtrimethanesul
Foxide (III), 1,1,1-tris (diethyl
(Sphinomethyl) ethane titanium trimethanesulfoxide
Titanium complex such as (III), tris (methoxymethyl)
Methane vanadium trimethanesulfoxide (III),
1,1,1-tris (methoxymethyl) ethanevanadium
Mutrimethanesulfoxide (III), 1,1,1-to
Squirrel (ethoxymethyl) ethanevanadium trimethanes
Rufoxide (III), 1,1,1-tris (butoxide
Methyl) ethanevanadium trimethanesulfoxide (I
II) 1,1,1-tris (phenoxymethyl) eta
Nb vanadium trimethanesulfoxide (III), tri
Furylmethane vanadium trimethanesulfoxide (II
I), 1,1,1-tris (methylthiomethyl) ethane
Vanadium trimethanesulfoxide (III), 1,
1,1-tris (dimethylaminomethyl) ethanevanadi
Trimethanesulfoxide (III), tris (pyra
Zolyl) methane vanadium trimethanesulfoxide (I
II), tris (3,5-dimethyl-1-pyrazolyl)
Methane vanadium trimethanesulfoxide (III),
1,1,1-tris (3,5-dimethyl-1-pyrazoli
Le) ethanevanadium trimethanesulfoxide (II
I), tris (3,5-diisopropyl-1-pyrazoli)
L) methane vanadium trimethanesulfoxide (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methane vanadium trimethanesulfoxide (III),
Tris (2-pyridyl) methane vanadium trimethanes
Rufoxide (III), tris (6-methyl-2-pyri
Jil) methane vanadium trimethanesulfoxide (II
I), tris (2-pyridyl) amine vanadium trime
Tansulfoxide (III), tris (1-imidazoli)
L) methane vanadium trimethanesulfoxide (II
I), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethanevanadium trimethanesulfoxide (II
I), 1,1,1-tris (diphenylphosphinomethyi)
Le) ethanevanadium trimethanesulfoxide (II
I), 1,1,1-tris (diethylphosphinomethyi)
Le) ethanevanadium trimethanesulfoxide (II
I) and other vanadium complexes, tris (methoxymethyl) meth
Tanchrome trimethanesulfoxide (III), 1,
1,1-tris (methoxymethyl) ethanechrome trime
Tansulfoxide (III), 1,1,1-tris (d
Toximethyl) ethanechrome trimethanesulfoxide
(III) 1,1,1-tris (butoxymethyl) d
Tanchrome trimethanesulfoxide (III), 1,
1,1-tris (phenoxymethyl) ethanechrome tri
Methanesulfoxide (III), trifurylmethane chloride
Mutrimethanesulfoxide (III), 1,1,1-to
Lis (methylthiomethyl) ethanechrome trimethanesul
Foxide (III), 1,1,1-tris (dimethyla
Minomethyl) ethanechrome trimethanesulfoxide (I
II), tris (pyrazolyl) methanechromium trimethane
Sulfoxide (III), tris (3,5-dimethyl-
1-pyrazolyl) methanechromium trimethanesulfoxide
(III), 1,1,1-tris (3,5-dimethyl-
1-pyrazolyl) ethanechrome trimethanesulfoxide
(III), tris (3,5-diisopropyl-1-pi
Lazolyl) methanechromium trimethanesulfoxide (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methanechrome trimethanesulfoxide (III), trimethane
(2-pyridyl) methanechromium trimethanesulfoxy
(III), tris (6-methyl-2-pyridyl) meth
Tanchrome trimethanesulfoxide (III), tris
(2-pyridyl) amine chromium trimethanesulfoxide
(III), tris (1-imidazolyl) methanechromium
Trimethanesulfoxide (III), 1,1,1-tri
(Dimethylphosphinomethyl) ethanechrome trimeta
Sulfoxide (III), 1,1,1-tris (dif
Enylphosphinomethyl) ethanechrome trimethanesul
Foxide (III), 1,1,1-tris (diethyl
(Sphinomethyl) ethanechrome trimethanesulfoxide
Chromium complex such as (III), tris (methoxymethyl)
Methane manganese trimethane sulfoxide (III),
1,1,1-tris (methoxymethyl) ethanemanganese
Trimethanesulfoxide (III), 1,1,1-tri
(Ethoxymethyl) ethanemanganese trimethanesulfo
Oxide (III), 1,1,1-tris (butoxymethi
Le) ethane manganese trimethanesulfoxide (II)
I), 1,1,1-tris (phenoxymethyl) ethane
Manganese trimethanesulfoxide (III), triflate
Methane manganese trimethane sulfoxide (III),
1,1,1-tris (methylthiomethyl) ethanemanga
Trimethanesulfoxide (III), 1,1,1-to
Lis (dimethylaminomethyl) ethanemanganese trimeta
Sulfoxide (III), tris (pyrazolyl) meta
Manganese trimethanesulfoxide (III), tris
(3,5-dimethyl-1-pyrazolyl) methanemanganese
Trimethanesulfoxide (III), 1,1,1-tri
(3,5-dimethyl-1-pyrazolyl) ethanemanga
Trimethanesulfoxide (III), tris (3,5
-Diisopropyl-1-pyrazolyl) methanemanganate
Limethane sulfoxide (III), tris (3,5-di
Phenyl-1-pyrazolyl) methanemanganesetrimethane
Sulfoxide (III), tris (2-pyridyl) meta
Manganese trimethanesulfoxide (III), tris
(6-Methyl-2-pyridyl) methanemanganese trimeta
Sulfoxide (III), tris (2-pyridyl) a
Min manganese trimethanesulfoxide (III), tri
(1-imidazolyl) methane manganese trimethanesulfur
Foxide (III), 1,1,1-tris (dimethylphos
(Sphinomethyl) ethanemanganesetrimethanesulfoxy
(III), 1,1,1-tris (diphenylphosphine
(Inomethyl) ethanemanganesetrimethanesulfoxide
(III), 1,1,1-tris (diethylphosphino)
Methyl) ethanemanganese trimethanesulfoxide (II
Manganese complex such as I), tris (methoxymethyl) meta
Iron trimethanesulfoxide (III), 1,1,1-
Tris (methoxymethyl) ethaneiron trimethanesulfonoxy
Sid (III), 1,1,1-tris (ethoxymethy
L) ethane iron trimethanesulfoxide (III), 1,
1,1-tris (butoxymethyl) ethane iron trimethane
Sulfoxide (III), 1,1,1-tris (pheno
Xymethyl) ethaneiron trimethanesulfoxide (II
I), trifurylmethaneiron trimethanesulfoxide (I
II) 1,1,1-tris (methylthiomethyl) eta
Iron trimethanesulfoxide (III), 1,1,1-
Tris (dimethylaminomethyl) ethaneiron trimethanes
Rufoxide (III), tris (pyrazolyl) methaneiron
Trimethanesulfoxide (III), tris (3,5-
Dimethyl-1-pyrazolyl) methaneiron trimethanesulfo
Oxide (III), 1,1,1-tris (3,5-dimethyl
Tyl-1-pyrazolyl) ethaneiron trimethanesulfoxy
(III), tris (3,5-diisopropyl-1-
Pyrazolyl) methaneiron trimethanesulfoxide (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methane iron trimethanesulfoxide (III), tris
(2-pyridyl) methaneiron trimethanesulfoxide (I
II), tris (6-methyl-2-pyridyl) methaneiron
Trimethanesulfoxide (III), tris (2-pyri
Gill) amine iron trimethanesulfoxide (III), g
Lis (1-imidazolyl) methaneiron trimethanesulfonate
Sid (III), 1,1,1-tris (dimethylphosphine
Inomethyl) ethaneiron trimethanesulfoxide (II
I), 1,1,1-tris (diphenylphosphinomethyi)
L) ethane iron trimethanesulfoxide (III), 1,
1,1-tris (diethylphosphinomethyl) ethaneiron
Iron complex such as trimethanesulfoxide (III), tris
(Methoxymethyl) methanecobalt trimethanesulfonoxy
Sid (III), 1,1,1-tris (methoxymethyl
Le) ethanecobalt trimethanesulfoxide (II)
I), 1,1,1-tris (ethoxymethyl) ethaneco
Baltotrimethanesulfoxide (III), 1,1,1
-Tris (butoxymethyl) ethanecobalttrimethane
Sulfoxide (III), 1,1,1-tris (pheno
(Xymethyl) ethanecobalt trimethanesulfoxide
(III), trifurylmethane cobalt trimethanesul
Foxide (III), 1,1,1-tris (methylthio
Methyl) ethanecobalt trimethanesulfoxide (II
I), 1,1,1-tris (dimethylaminomethyl)
Tancobalt trimethanesulfoxide (III), tri
S (pyrazolyl) methanecobalt trimethanesulfoxy
(III), tris (3,5-dimethyl-1-pyrazo)
Ril) methanecobalt trimethanesulfoxide (II
I), 1,1,1-tris (3,5-dimethyl-1-pi
Lazolyl) ethanecobalt trimethanesulfoxide (I
II), tris (3,5-diisopropyl-1-pyrazo)
Ril) methanecobalt trimethanesulfoxide (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methanecobalt trimethanesulfoxide (III),
Lis (2-pyridyl) methanecobalt trimethanesulfo
Oxide (III), tris (6-methyl-2-pyridyl)
B) methanecobalt trimethanesulfoxide (II
I), tris (2-pyridyl) amine cobalt trimeta
Sulfoxide (III), tris (1-imidazoli)
B) methanecobalt trimethanesulfoxide (II
I), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethanecobalt trimethanesulfoxide (II)
I), 1,1,1-tris (diphenylphosphinomethyi)
Le) ethanecobalt trimethanesulfoxide (II)
I), 1,1,1-tris (diethylphosphinomethyi)
Le) ethanecobalt trimethanesulfoxide (III)
Cobalt complexes such as tris (methoxymethyl) methane
Cockel trimethanesulfoxide (III), 1,1,1
-Tris (methoxymethyl) ethane nickel trimethane
Sulfoxide (III), 1,1,1-tris (ethoxy
Cimethyl) ethane nickel trimethanesulfoxide (I
II), 1,1,1-tris (butoxymethyl) ethane
Nickel trimethanesulfoxide (III), 1,1,
1-tris (phenoxymethyl) ethane nickel trim
Tansulfoxide (III), trifurylmethane nickel
Rutrimethanesulfoxide (III), 1,1,1-to
Lis (methylthiomethyl) ethane nickel trimethanes
Rufoxide (III), 1,1,1-tris (dimethyl
Aminomethyl) ethane nickel trimethanesulfoxide
(III), tris (pyrazolyl) methane nickel tri
Methanesulfoxide (III), tris (3,5-dimethyl
Tyl-1-pyrazolyl) methane nickel trimethanesul
Foxide (III), 1,1,1-tris (3,5-di
Methyl-1-pyrazolyl) ethane nickel trimethanes
Rufoxide (III), tris (3,5-diisopropyl
Ru-1-pyrazolyl) methane nickel trimethanesulfo
Oxide (III), tris (3,5-diphenyl-1-
Pyrazolyl) methane nickel trimethane sulfoxide
(III), tris (2-pyridyl) methane nickel oxide
Limethane sulfoxide (III), tris (6-methyl
-2-pyridyl) methane nickel trimethanesulfoxy
(III), tris (2-pyridyl) amine nickel
Trimethanesulfoxide (III), tris (1-imi
Dazolyl) methane nickel trimethanesulfoxide (I
II), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethane nickel trimethanesulfoxide (II
I), 1,1,1-tris (diphenylphosphinomethyi)
Le) ethane nickel trimethanesulfoxide (II
I), 1,1,1-tris (diethylphosphinomethyi)
Le) ethane nickel trimethanesulfoxide (III)
Nickel complexes such as tris (pyrazolyl) methaneit
Lium trimethanesulfoxide (III), Tris
(3,5-dimethyl-1-pyrazolyl) methane yttria
Umtrimethanesulfoxide (III), 1,1,1-
Tris (3,5-dimethyl-1-pyrazolyl) ethane
Thorium trimethanesulfoxide (III), Tris
(3,5-diisopropyl-1-pyrazolyl) methanei
Thorium trimethanesulfoxide (III), Tris
(3,5-diphenyl-1-pyrazolyl) methaneit
Yttria such as lium trimethanesulfoxide (III)
Complex, tris (pyrazolyl) methanemolybdenumtri
Methanesulfoxide (III), tris (3,5-dimethyl
Tyl-1-pyrazolyl) methanemolybdenumtrimethanes
Rufoxide (III), 1,1,1-tris (3,5-
Dimethyl-1-pyrazolyl) ethanemolybdenum trimeta
Sulfoxide (III), tris (3,5-diisopropane)
Ropyl-1-pyrazolyl) methanemolybdenumtrimethane
Sulfoxide (III), tris (3,5-diphenyl
-1-pyrazolyl) methanemolybdenumtrimethanesulfo
Molybdenum complexes such as oxide (III), tris (pyrazo
Ril) methaneruthenium trimethanesulfoxide (II
I), tris (3,5-dimethyl-1-pyrazolyl) me
Tanruthenium trimethanesulfoxide (III),
1,1,1-tris (3,5-dimethyl-1-pyrazoli
Le) ethane ruthenium trimethanesulfoxide (II)
I), tris (3,5-diisopropyl-1-pyrazoli)
Le) methaneruthenium trimethanesulfoxide (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methaneruthenium trimethanesulfoxide (III), etc.
Ruthenium complex, tris (pyrazolyl) methandrhodium
Mutrimethanesulfoxide (III), Tris (3,5
-Dimethyl-1-pyrazolyl) methane rhodium trimeta
Sulfoxide (III), 1,1,1-tris (3,
5-dimethyl-1-pyrazolyl) ethane rhodium trime
Tansulfoxide (III), tris (3,5-diiso
Propyl-1-pyrazolyl) methanerhodiumtrimethane
Sulfoxide (III), tris (3,5-diphenyl
-1-pyrazolyl) methane rhodium trimethane sulfoxy
Coordination of neutral ligands such as rhodium complexes such as sido (III)
Tris (methoxymethyl)
M) methanescandium tris (diethylamide) (I
II) 1,1,1-tris (methoxymethyl) ethane
Scandium tris (diethylamide) (III),
1,1,1-tris (ethoxymethyl) ethanescandi
Umtris (diethylamide) (III), 1,1,1
-Tris (butoxymethyl) ethanescandium tris
(Diethylamide) (III), 1,1,1-tris
(Phenoxymethyl) ethanescandium tris (die
Tylamide) (III), trifurylmethanescandiu
Mutris (diethylamide) (III), 1,1,1-
Tris (methylthiomethyl) ethanescandium tris
(Diethylamide) (III), 1,1,1-tris
(Dimethylaminomethyl) ethanescandium tris
(Diethylamide) (III), tris (pyrazolyl)
Methane scandium tris (diethylamide) (II
I), tris (3,5-dimethyl-1-pyrazolyl) me
Tanscandium tris (diethylamide) (II
I), 1,1,1-tris (3,5-dimethyl-1-pi
Lazolyl) ethanescandium tris (diethylamido)
De) (III), tris (3,5-diisopropyl-1)
-Pyrazolyl) methanescandium tris (diethylamine)
Mido) (III), tris (3,5-diphenyl-1-)
Pyrazolyl) methane scandium tris (diethylamido)
Do) (III), tris (2-pyridyl) methanescan
Dium tris (diethylamide) (III), Tris
(6-methyl-2-pyridyl) methane scandium tri
(Diethylamide) (III), tris (2-pyridi
A) Amine scandium tris (diethylamide) (I
II), tris (1-imidazolyl) methanescandiu
Mutris (diethylamide) (III), 1,1,1-
Tris (dimethylphosphinomethyl) ethanescandiu
Mutris (diethylamide) (III), 1,1,1-
Tris (diphenylphosphinomethyl) ethane scandi
Umtris (diethylamide) (III), 1,1,1
-Tris (diethylphosphinomethyl) ethanescandi
Scandi such as umtris (diethylamide) (III)
Complex, tris (methoxymethyl) methane titanium tri
(Diethylamide) (III), 1,1,1-tris
(Methoxymethyl) ethane titanium tris (diethylamido)
Do) (III), 1,1,1-tris (ethoxymethy
R) ethane titanium tris (diethylamide) (II)
I), 1,1,1-tris (butoxymethyl) ethane
Tantris (diethylamide) (III), 1,1,1
-Tris (phenoxymethyl) ethane titanium tris (di
Ethylamide) (III), trifurylmethane titanate
Squirrel (diethylamide) (III), 1,1,1-tri
Tris (methylthiomethyl) ethane titanium tris (diethyl
Amide) (III), 1,1,1-tris (dimethyla
Minomethyl) ethane titanium tris (diethylamide)
(III), tris (pyrazolyl) methane titanium tris
(Diethylamide) (III), tris (3,5-dimethyl)
Tyl-1-pyrazolyl) methanetitanium tris (diethyl)
Amide) (III), 1,1,1-tris (3,5-di
Methyl-1-pyrazolyl) ethane titanium tris (diethyl
Rumid) (III), tris (3,5-diisopropyl)
Ru-1-pyrazolyl) methanetitanium tris (diethylamine)
Mido) (III), tris (3,5-diphenyl-1-)
Pyrazolyl) methane titanium tris (diethylamide)
(III), tris (2-pyridyl) methane titanium tri
(Diethylamide) (III), tris (6-methyl)
-2-pyridyl) methanetitanium tris (diethylamido)
(III), tris (2-pyridyl) amine titanium
Tris (diethylamide) (III), tris (1-a
Midazolyl) methane titanium tris (diethylamide)
(III), 1,1,1-tris (dimethylphosphino
Methyl) ethane titanium tris (diethylamide) (II
I), 1,1,1-tris (diphenylphosphinomethyi)
R) ethane titanium tris (diethylamide) (II)
I), 1,1,1-tris (diethylphosphinomethyi)
R) ethane titanium tris (diethylamide) (III)
Titanium complex such as tris (methoxymethyl) methanebana
Diumtris (diethylamide) (III), 1,1,
1-tris (methoxymethyl) ethanevanadium tris
(Diethylamide) (III), 1,1,1-tris
(Ethoxymethyl) ethanevanadium tris (diethyl
Amide) (III), 1,1,1-tris (butoxime
Chill) ethanevanadium tris (diethylamide) (I
II) 1,1,1-tris (phenoxymethyl) eta
Nvanadium tris (diethylamide) (III),
Refurylmethane vanadium tris (diethylamide)
(III), 1,1,1-tris (methylthiomethyl)
Ethanevanadium tris (diethylamide) (II
I), 1,1,1-tris (dimethylaminomethyl)
Tamvanadium tris (diethylamide) (III),
Tris (pyrazolyl) methane vanadium tris (diethyl
Ruamide) (III), tris (3,5-dimethyl-1)
-Pyrazolyl) methanevanadium tris (diethylamido)
(III), 1,1,1-tris (3,5-dimethyl)
Ru-1-pyrazolyl) ethanevanadium tris (diethyl
Rumid) (III), tris (3,5-diisopropyl)
Ru-1-pyrazolyl) methane vanadium tris (diethyl
Ruamide) (III), tris (3,5-diphenyl-
1-pyrazolyl) methane vanadium tris (diethyla
Mido) (III), tris (2-pyridyl) methanebana
Dium tris (diethylamide) (III), Tris
(6-Methyl-2-pyridyl) methane vanadium tris
(Diethylamide) (III), tris (2-pyridi
I) Amine vanadium tris (diethylamide) (II
I), tris (1-imidazolyl) methanevanadium
Squirrel (diethylamide) (III), 1,1,1-tri
(Dimethylphosphinomethyl) ethanevanadium tri
(Diethylamide) (III), 1,1,1-tris
(Diphenylphosphinomethyl) ethanevanadium tri
(Diethylamide) (III), 1,1,1-tris
(Diethylphosphinomethyl) ethanevanadium tris
Vanadium complexes such as (diethylamide) (III)
Lis (methoxymethyl) methanechromium tris (diethyl
Amide) (III), 1,1,1-tris (methoxymeth
Tyl) ethanechrome tris (diethylamide) (II
I), 1,1,1-tris (ethoxymethyl) ethane tank
Lomtris (diethylamide) (III), 1,1,1
-Tris (butoxymethyl) ethanechrome tris (die
(III), 1,1,1-tris (pheno)
(Xymethyl) ethanechrome tris (diethylamide)
(III), trifurylmethanechromium tris (diethyl
Amide) (III), 1,1,1-tris (methylthio
Methyl) ethanechrome tris (diethylamide) (II
I), 1,1,1-tris (dimethylaminomethyl)
Tanchrome tris (diethylamide) (III), tri
Tris (pyrazolyl) methanechromium tris (diethylamido)
Do) (III), tris (3,5-dimethyl-1-pyra)
Zolyl) methanechromium tris (diethylamide) (II
I), 1,1,1-tris (3,5-dimethyl-1-pi
Lazolyl) ethanechrome tris (diethylamide) (I
II), tris (3,5-diisopropyl-1-pyrazo)
Ryl) methanechromium tris (diethylamide) (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methanechromium tris (diethylamide) (III),
Lis (2-pyridyl) methanechromium tris (diethylamine)
Mido) (III), Tris (6-methyl-2-pyridi)
L) methanechromium tris (diethylamide) (II
I), tris (2-pyridyl) amine chromium tris (di
Ethylamide) (III), Tris (1-imidazoli)
L) methanechromium tris (diethylamide) (II
I), 1,1,1-tris (dimethylphosphinomethyi)
R) ethanechrome tris (diethylamide) (II)
I), 1,1,1-tris (diphenylphosphinomethyi)
R) ethanechrome tris (diethylamide) (II)
I), 1,1,1-tris (diethylphosphinomethyi)
R) ethanechrome tris (diethylamide) (III)
Chromium complex such as tris (methoxymethyl) methane man
Gantris (diethylamide) (III), 1,1,1
-Tris (methoxymethyl) ethanemanganese tris (di
Ethylamide) (III), 1,1,1-tris (etho
(Methyl) ethanemanganese tris (diethylamide)
(III) 1,1,1-tris (butoxymethyl) d
Tanmanganese tris (diethylamide) (III),
1,1,1-tris (phenoxymethyl) ethanemanga
Tris (diethylamide) (III), trifurylme
Tanmanganese tris (diethylamide) (III),
1,1,1-tris (methylthiomethyl) ethanemanga
Tris (diethylamide) (III), 1,1,1-
Tris (dimethylaminomethyl) ethanemanganese tris
(Diethylamide) (III), tris (pyrazolyl)
Methanemanganese tris (diethylamide) (III),
Tris (3,5-dimethyl-1-pyrazolyl) methane
Gantris (diethylamide) (III), 1,1,
1-tris (3,5-dimethyl-1-pyrazolyl) ethane
Manganese tris (diethylamide) (III)
(3,5-diisopropyl-1-pyrazolyl) methane
Manganese tris (diethylamide) (III), tris
(3,5-diphenyl-1-pyrazolyl) methanemanganese
Tris (diethylamide) (III), Tris (2-
Pyridyl) methanemanganese tris (diethylamide)
(III), tris (6-methyl-2-pyridyl) meta
Manganese tris (diethylamide) (III)
Tris (2-pyridyl) amine manganese tris
Mido) (III), tris (1-imidazolyl) methane
Manganese tris (diethylamide) (III), 1,
1,1-tris (dimethylphosphinomethyl) ethanema
Gantris (diethylamide) (III), 1,1,
1-tris (diphenylphosphinomethyl) ethaneman
Gantris (diethylamide) (III), 1,1,1
-Tris (diethylphosphinomethyl) ethanemanganese
Manganese complex such as tris (diethylamide) (III)
Body, tris (methoxymethyl) methaneiron tris (diethyl
Lumido) (III), 1,1,1-tris (methoxy)
Methyl) ethaneiron tris (diethylamide) (II
I), 1,1,1-tris (ethoxymethyl) ethaneiron
Tris (diethylamide) (III), 1,1,1-to
Lis (butoxymethyl) ethane iron tris (diethylamido)
Do) (III), 1,1,1-tris (phenoxymethi
R) ethane iron tris (diethylamide) (III),
Refurylmethane iron tris (diethylamide) (II
I), 1,1,1-tris (methylthiomethyl) ethane
Iron tris (diethylamide) (III), 1,1,1-
Tris (dimethylaminomethyl) ethane iron tris (die
Tylamide) (III), tris (pyrazolyl) methane
Iron tris (diethylamide) (III), tris (3
5-dimethyl-1-pyrazolyl) methaneiron tris (die
(III), 1,1,1-tris (3,5
-Dimethyl-1-pyrazolyl) ethaneiron tris (diethyl
Rumid) (III), tris (3,5-diisopropyl)
Ru-1-pyrazolyl) methaneiron tris (diethylamido)
(III), tris (3,5-diphenyl-1-pi
Lazolyl) methaneiron tris (diethylamide) (II
I), tris (2-pyridyl) methaneiron tris (diethyl)
Ruamide) (III), tris (6-methyl-2-pyri)
Jill) methaneiron tris (diethylamide) (III),
Tris (2-pyridyl) amine iron tris (diethylamido)
Do) (III), tris (1-imidazolyl) methaneiron
Tris (diethylamide) (III), 1,1,1-to
Lis (dimethylphosphinomethyl) ethaneiron tris (di
Ethylamide) (III), 1,1,1-tris (diff
Phenylphosphinomethyl) ethaneiron tris (diethylamine)
Amide) (III), 1,1,1-tris (diethylphos
Finomethyl) ethaneiron tris (diethylamide) (I
II) and other iron complexes, tris (methoxymethyl) methaneco
Bartotris (diethylamide) (III), 1,1,
1-tris (methoxymethyl) ethane cobalt tris
(Diethylamide) (III), 1,1,1-tris
(Ethoxymethyl) ethanecobalt tris (diethylamine)
Mido) (III), 1,1,1-tris (butoxymethi
Le) ethanecobalt tris (diethylamide) (II)
I), 1,1,1-tris (phenoxymethyl) ethane
Cobalt tris (diethylamide) (III), torif
Rylmethanecobalt tris (diethylamide) (II
I), 1,1,1-tris (methylthiomethyl) ethane
Cobalt tris (diethylamide) (III), 1,
1,1-tris (dimethylaminomethyl) ethanecobal
Totris (diethylamide) (III), Tris (pyra
Zolyl) methanecobalt tris (diethylamide) (I
II), tris (3,5-dimethyl-1-pyrazolyl)
Methanecobalt tris (diethylamide) (III),
1,1,1-tris (3,5-dimethyl-1-pyrazoli
Le) ethanecobalt tris (diethylamide) (II)
I), tris (3,5-diisopropyl-1-pyrazoli)
L) methanecobalt tris (diethylamide) (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methanecobalt tris (diethylamide) (III),
Tris (2-pyridyl) methanecobalt tris (diethyl
Ruamide) (III), tris (6-methyl-2-pyri)
(Zyl) methanecobalt tris (diethylamide) (II
I), tris (2-pyridyl) amine cobalt tris
(Diethylamide) (III), tris (1-imidazo
Ril) methanecobalt tris (diethylamide) (II
I), 1,1,1-tris (dimethylphosphinomethyi)
Le) ethanecobalt tris (diethylamide) (II)
I), 1,1,1-tris (diphenylphosphinomethyi)
Le) ethanecobalt tris (diethylamide) (II)
I), 1,1,1-tris (diethylphosphinomethyi)
Le) ethanecobalt tris (diethylamide) (II)
I) and other cobalt complexes, tris (methoxymethyl) meta
Nickel tris (diethylamide) (III), 1,
1,1-tris (methoxymethyl) ethane nickel tri
(Diethylamide) (III), 1,1,1-tris
(Ethoxymethyl) ethane nickel tris
Mido) (III), 1,1,1-tris (butoxymethi
L) ethane nickel tris (diethylamide) (II)
I), 1,1,1-tris (phenoxymethyl) ethane
Nickel tris (diethylamide) (III), torif
Rylmethane nickel tris (diethylamide) (II
I), 1,1,1-tris (methylthiomethyl) ethane
Nickel tris (diethylamide) (III), 1,
1,1-tris (dimethylaminomethyl) ethane nickel
Lutris (diethylamide) (III), tris (pyra
Zolyl) methane nickel tris (diethylamide) (I
II), tris (3,5-dimethyl-1-pyrazolyl)
Methane nickel tris (diethylamide) (III),
1,1,1-tris (3,5-dimethyl-1-pyrazoli
L) ethane nickel tris (diethylamide) (II)
I), tris (3,5-diisopropyl-1-pyrazoli)
L) methane nickel tris (diethylamide) (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methane nickel tris (diethylamide) (III),
Tris (2-pyridyl) methane nickel tris (diethyl
Ruamide) (III), tris (6-methyl-2-pyri)
(Zyl) methane nickel tris (diethylamide) (II
I), tris (2-pyridyl) amine nickel tris
(Diethylamide) (III), tris (1-imidazo
Ril) methane nickel tris (diethylamide) (II
I), 1,1,1-tris (dimethylphosphinomethyi)
L) ethane nickel tris (diethylamide) (II)
I), 1,1,1-tris (diphenylphosphinomethyi)
L) ethane nickel tris (diethylamide) (II)
I), 1,1,1-tris (diethylphosphinomethyi)
L) ethane nickel tris (diethylamide) (II)
I) and other nickel complexes, tris (pyrazolyl) methane
Thorium tris (diethylamide) (III), tri
(3,5-dimethyl-1-pyrazolyl) methaneit
Lithium tris (diethylamide) (III), 1,1,
1-tris (3,5-dimethyl-1-pyrazolyl) ethane
Yttrium tris (diethylamide) (III),
Tris (3,5-diisopropyl-1-pyrazolyl) meth
Yttrium tris (diethylamide) (II
I), tris (3,5-diphenyl-1-pyrazolyl)
Methane yttrium tris (diethylamide) (II
Yttrium complex such as I), tris (pyrazolyl) meta
Nmolybdenum tris (diethylamide) (III),
Squirrel (3,5-dimethyl-1-pyrazolyl) methanemori
Budentris (diethylamide) (III), 1,1,
1-tris (3,5-dimethyl-1-pyrazolyl) ethane
Nmolybdenum tris (diethylamide) (III),
Lis (3,5-diisopropyl-1-pyrazolyl) meta
Nmolybdenum tris (diethylamide) (III),
Lis (3,5-diphenyl-1-pyrazolyl) methanemo
Molybdenum such as ribdentris (diethylamide) (III)
Budene complex, tris (pyrazolyl) methane ruthenium ton
Squirrel (diethylamide) (III), tris (3,5-
Dimethyl-1-pyrazolyl) methaneruthenium tris
(Diethylamide) (III), 1,1,1-tris
(3,5-dimethyl-1-pyrazolyl) ethaneruthenium
Mutris (diethylamide) (III), Tris (3,
5-diisopropyl-1-pyrazolyl) methaneruthenium
Mutris (diethylamide) (III), Tris (3,
5-diphenyl-1-pyrazolyl) methaneruthenium trioxide
Ruthenium complex such as lith (diethylamide) (III)
Body, tris (pyrazolyl) methane rhodium tris (die
Tylamide) (III), tris (3,5-dimethyl-
1-pyrazolyl) methanerhodium tris (diethylamido)
(III), 1,1,1-tris (3,5-dimethyl)
Ru-1-pyrazolyl) ethane rhodium tris (diethyl)
Amide) (III), tris (3,5-diisopropyl)
-1-pyrazolyl) methandrhodium tris (diethyla
Mido) (III), tris (3,5-diphenyl-1-)
Pyrazolyl) methandhodium tris (diethylamide)
A neutral ligand such as a rhodium complex such as (III) is coordinated
Amide transition metal complexes can be mentioned.

From the viewpoint of catalytic activity, chromium metal is preferred as the transition metal, and the valence of chromium metal is preferably trivalent. As the neutral polydentate ligand having a tripod-type structure represented by the general formula (1), nitrogen-containing tridentate ligands having a heterocyclic group are preferably used, and more preferably tris (3 , 5-Dimethyl-1-pyrazolyl) methane is used. X is preferably a halogen atom. Tris (3,5-dimethyl-1-pyrazolyl) methanechrome trichloride (III) is used as a transition metal complex coordinated with a neutral polydentate ligand having a more preferable tripod structure.

In the present invention, the method for synthesizing the transition metal complex having the above-described neutral polydentate ligand having a tripod-type structure coordinated is not particularly limited. A known complex formation method with a transition metal compound [for example, In
org. Chem. , 25, 1080 (1986), etc.]
Can be easily synthesized. In this case, the transition metal compound that can be used is not particularly limited. For example, scandium (III) chloride, scandium (III) bromide, scandium (III) iodide,
Titanium (III) chloride, tris (tetrahydrofuran)
Titanium trichloride (III), vanadium chloride (I
II), tris (tetrahydrofuran) vanadium trichloride (III), vanadium (III) bromide, vanadium (III) iodide, vanadium fluoride (II)
I), chromium (III) chloride, chromium (II) chloride, chromium (III) bromide, chromium (II) bromide, chromium (III) iodide, chromium (II) iodide, chromium (III) fluoride, Chromium (II) fluoride, tris (tetrahydrofuran) chromium trichloride (III), tris (1,4-dioxane) chromium trichloride (II
I), tris (diethyl ether) chromium trichloride (III), tris (pyridine) chromium trichloride (III), tris (acetonitrile) chromium trichloride (III), manganese chloride (III), manganese (III) bromide, Manganese (III) iodide, manganese (III) fluoride, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) fluoride, cobalt (II) iodide, iron (III) chloride, iron chloride ( II), iron (III) bromide, iron (II) bromide, iron (III) iodide,
Iron (III) fluoride, nickel (II) chloride, yttrium (III) fluoride, yttrium (III) chloride,
Yttrium (III) bromide, Yttrium iodide (I
II), molybdenum (III) chloride, molybdenum (III) bromide, rhodium (III) chloride, rhodium (III) bromide, ruthenium (III) chloride, ruthenium (III) bromide and the like.

The concentration of the transition metal when the polydentate ligand is reacted with the transition metal compound to form a transition metal complex is not particularly limited. The solvent used here is not particularly limited, but an organic solvent is preferably used. For example, pentane, hexane, heptane,
Aliphatic hydrocarbons such as octane, nonane, decane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and trimethylbenzene; ethers such as diethyl ether and tetrahydrofuran; methylene chloride; chloroform; And halogenated hydrocarbons such as carbon chloride. In addition, each of the above solvents can be used alone, or two or more of them can be used as a mixture.

The complex formation reaction is carried out at any temperature from -80 ° C to the boiling point of the reaction solvent used, preferably at 20 to 200 ° C. When the complex formation reaction is performed at a temperature equal to or higher than the boiling point of the reaction solvent, it can be performed under pressure. The reaction time is not particularly limited, and is usually 1 minute to 48 hours,
Preferably it is 5 minutes to 24 hours. It is desirable that all operations during the reaction be performed while avoiding air and moisture. Further, it is preferable that the raw materials and the solvent are sufficiently dried.

The transition metal complex to which the polydentate ligand is coordinated usually precipitates as a solid, and can be separated from the reaction solvent by filtration. Further, if necessary, after washing with the above-mentioned solvent, vacuum drying is performed to synthesize a transition metal complex which is one of the constituent components of the ethylene trimerization catalyst.
If no precipitation occurs, precipitation can be performed by distilling off the solvent, adding a poor solvent, or cooling.

In the present invention, among the transition metal complexes coordinated by a neutral polydentate ligand having a tripod-type structure, a transition metal complex in which the polydentate ligand is coordinated with a factor is used. preferable. By using a transition metal complex in which a polydentate ligand is coordinated with a factor, effects such as suppression of by-product of polyethylene are remarkably recognized. here,
A complex in which a polydentate ligand is coordinated to a facial is one of isomers of a hexacoordinate octahedral complex in which three coordination sites are occupied by a polydentate ligand [Chemical Selection Organometallic] Chemistry: Basics and Applications, p. 143 (Shokabo)]. That is, in a six-coordinate octahedral complex in which three coordination sites are occupied by a multidentate ligand, the multidentate ligands are coordinated in an arrangement such that the three coordination sites are cis with respect to each other. Means you are.

The alkyl metal compound used in the present invention is not particularly limited. For example, the following general formula (4) R _p M′X _q (4) (where p is 0 <p ≦ 3, q is 0 ≦ q <3, and p + q is 1 to 3. M ′ represents lithium, magnesium, zinc, boron or aluminum;
R represents one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, and X represents one or more selected from the group consisting of a hydrogen atom, an alkoxide group, an aryl group and a halogen atom. Compounds represented by the formula (1) are preferred.

In the above general formula (4), the number of carbon atoms is 1 to 1.
The alkyl group of 0 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and an octyl group. The alkoxide group is not particularly limited, but examples include a methoxide group, an ethoxide group, a butoxide group, and a phenoxide group. The aryl group is not particularly limited, but includes, for example, a phenyl group. The halogen atom is not particularly limited, but includes, for example, fluorine, chlorine, bromine and iodine.

In the general formula (4), when M ′ is Al and p and q are each 1.5, AlR _1.5 X
_1.5 . Although such compounds do not exist in theory, they are usually conventionally expressed as sesqui-forms of Al ₂ R ₃ X ₃ , and these compounds are also included in the present invention.

Examples of the alkyl metal compound represented by the general formula (4) include, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, diethyl magnesium, ethyl butyl magnesium , Ethylchloromagnesium, ethylbromomagnesium, dimethylzinc, diethylzinc, dibutylzinc, trimethylborane, triethylborane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tricyclohexyl Aluminum, dimethylethylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethyl Rumi bromide phenoxide, dicyclohexyl phenyl aluminum, ethyl aluminum ethoxy chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, dicyclohexyl aluminum chloride,
Examples include methylaluminum sesquichloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like.

Of these, alkyl aluminum compounds are preferably used in view of availability and activity.
More preferably, triethylaluminum or triisobutylaluminum is used. These alkyl metal compounds can be used alone or in combination of two or more.

The amount of the alkyl metal compound to be used is 0.1 to 10000 equivalents, preferably 3 to 3000 equivalents, more preferably 5 to 200 equivalents, per mol of the transition metal complex.
It is 0 equivalent.

The radical anion used in the present invention is not particularly limited. For example, the following general formula (5): Ar ^{− ·} M ″ ⁺ (5) 6) represents at least one or more selected from (8)

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

(Wherein R1 to R28 each independently represent
A substituent containing a hydrogen atom, an element of group 13, 14, 15 or 16 of the periodic table, wherein two adjacent substituents may form a cyclic structure or an aromatic ring;
The carbon atom on the aromatic ring at the r site is group 15 or 1 in the periodic table
It also includes the case where the compound is a hetero element-containing compound substituted with a Group 6 element. ) And M ″ represent one or more metals selected from alkali metals and alkaline earth metals. Compounds represented by the formula (1) are preferred.

The Ar compound represented by the general formula (5) is not particularly restricted but includes, for example, biphenyl, fluorene, 4,4'-di (t-butyl) biphenyl, 9H-pyrido [3, 4-b] biphenyl derivatives such as indole, naphthalene, 1- (N, N-dimethylamino) naphthalene, naphthalene derivatives such as quinoline, anthracene, 9,10-dimethylanthracene, 3,4-
Examples include anthracene derivatives such as benzopyrene, 2,3-benzofluorene, 1,2-benzodiphenylene sulfide, acridine, and 3,6-bis (dimethylamino) acridine.

Examples of M ″ in the general formula (5) include alkali metals such as lithium, sodium and potassium and alkaline earth metals such as magnesium.

These radical anions can be prepared by known methods.
According to [for example, New Experimental Chemistry Course 12, p. 43 (Maruzen)], the compound can be easily synthesized by contacting the above-mentioned Ar compound with an alkali metal or alkaline earth metal in an ether solvent or the like.

As such radical anions, sodium naphthalene, sodium biphenyl, lithium (1
-(N, N-dimethylamino) naphthalene), sodium (1- (N, N-dimethylamino) naphthalene), potassium (1- (N, N-dimethylamino) naphthalene), lithium (4,4'-di (T-butyl) biphenyl), magnesium anthracene and the like. Of these, sodium naphthalene and sodium (1-
(N, N-dimethylamino) naphthalene) is preferably used.

The radical anion is used in an amount of 0.1 to 10 times, preferably 1.5 to 5 times, 1 mole of the transition metal complex coordinated with a neutral polydentate ligand having a tripod structure.
The range is twice as high.

The ethylene trimerization catalyst of the present invention comprising a transition metal complex coordinated with a neutral polydentate ligand having a tripod-type structure, an alkyl metal compound and a radical anion is provided by the above transition metal complex and alkyl metal It can be prepared by bringing a compound and a radical anion into contact with a raw material in a solvent. The contact method is not particularly limited.

The concentration of the transition metal complex in preparing this catalyst is not particularly limited, but is usually 0.03 per liter of the solvent.
01 micromolar to 100 mmol, preferably 0.0
Used at concentrations of 1 micromolar to 10 millimolar. If the catalyst concentration is lower than this, sufficient activity cannot be obtained. Conversely, if the catalyst concentration is higher than this, the catalyst activity does not increase and it is not economical. Further, as the solvent used here, for example, butane, pentane, hexane, heptane, octane, isooctane, nonane, decane, cyclopentane,
Aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane and decalin; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, trimethylbenzene, chlorobenzene and dichlorobenzene; methylene chloride, chloroform and carbon tetrachloride And chlorinated hydrocarbons such as dichloroethane. Further, a reaction product, that is, 1-hexene, can be used as a solvent. These solvents can be used alone or in combination of two or more. Here, for the purpose of controlling the transition metal complex concentration during the ethylene trimerization reaction, concentration and dilution may be performed as necessary.

The temperature at which the transition metal complex is brought into contact with the alkyl metal compound is -100 to 250 ° C, preferably 0 to 200 ° C. The contact time is not particularly limited, and is 1 minute to 24 hours, preferably 2 minutes to 2 hours.
It is desirable that all operations during contact be performed while avoiding air and moisture. Further, it is preferable that the raw materials and the solvent are sufficiently dried.

The ethylene trimerization reaction of the present invention can be carried out by bringing ethylene into contact with a catalyst comprising the above transition metal complex, an alkyl metal compound and a radical anion. Although the contact method is not particularly limited, for example, in the presence of ethylene which is a raw material of the trimerization reaction, a transition metal complex is contacted with an alkyl metal compound and a radical anion, and a method of starting the trimerization reaction simultaneously with the contact,
Alternatively, a method in which a transition metal complex is brought into contact with an alkyl metal compound and a radical anion in advance and then brought into contact with ethylene to carry out a trimerization reaction is employed. Specifically, in the former case, (1) a transition metal complex, an alkyl metal compound,
(2) introducing a transition metal complex, a radical anion and ethylene into a solution containing an alkyl metal compound, and (3) introducing a transition metal complex and a radical anion into a solution containing an alkyl metal compound. Introducing an alkyl metal compound and ethylene,
In this manner, the trimerization reaction of ethylene can be carried out. In the latter case, (1) an alkyl metal compound is introduced into a solution containing a transition metal complex and a radical anion, and then contacted with ethylene. (2) A transition metal complex and a radical anion are added to a solution containing an alkyl metal compound. After the introduction, the trimerization reaction of ethylene can be performed by a method of contacting with ethylene. The order of mixing these raw materials is not particularly limited.

The temperature of the ethylene trimerization reaction in the present invention is from -100 to 250 ° C., preferably from 0 to 2 ° C.
00 ° C. The reaction pressure is not particularly limited as long as the reaction system is in an ethylene atmosphere.
3000 kg / cm ² , preferably 0.1 to 30
It is 0 kg / cm ² . The reaction time depends on the temperature and the pressure and cannot be determined unconditionally, but is usually 5 seconds to 6 hours. Further, ethylene may be continuously supplied so as to maintain the above-mentioned pressure, or may be sealed at the above-mentioned pressure at the start of the reaction to cause a reaction. Ethylene as a raw material gas includes a gas inert to the reaction, for example, nitrogen, argon,
Helium or the like may be contained at all. In addition,
It is desirable that all operations in the ethylene trimerization reaction be performed while avoiding air and moisture. Further, it is preferable that ethylene is sufficiently dried.

This reaction can be carried out in any of a batch system, a semi-batch system and a continuous system. After completion of the ethylene trimerization reaction, the reaction can be stopped by adding a deactivator such as water, alcohol, or an aqueous sodium hydroxide solution to the reaction solution. The deactivated waste transition metal catalyst can be removed by a known deashing method, for example, extraction with water or an aqueous alkaline solution. The generated 1-hexene is separated from the reaction solution by a known extraction method or distillation method. In addition, polyethylene as a by-product can be separated and removed at the reaction solution outlet as a residue when a known centrifugal separation method or 1-hexene is separated by distillation.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are only for illustrating the outline of the present invention and the present invention is not limited to these Examples.

IR measurement: IR was measured by the Nujol method using an infrared spectrophotometer (FTIR-8100) manufactured by Shimadzu Corporation.

Analysis by Gas Chromatography: The amount of the product having 4 to 8 carbon atoms contained in the reaction solution was determined using a gas chromatograph (GC-14A) manufactured by Shimadzu Corporation equipped with a column of OV-1 manufactured by GL Science. And analyzed. The analysis conditions were set at an injection temperature of 280 ° C. and a detector temperature of 280 ° C. using a nitrogen carrier, and n-heptane was used as an internal standard. The analysis was performed by injecting 1.0 μl of the reaction solution into the gas chromatograph and then raising the temperature of the column from 40 ° C. to 250 ° C.

The product having 10 or more carbon atoms was obtained from GL Science, which was separately prepared from the above gas chromatograph.
Analysis was performed using a gas chromatograph (GC-14A) manufactured by Shimadzu Corporation equipped with an OV-1 column. The analysis was performed using a nitrogen carrier at an injection temperature of 300.
℃, detector temperature 300 ℃, n- as internal standard
Heptane was used. In the analysis, after injecting 1.5 μl of the reaction solution into this gas chromatograph, the temperature of the column was raised to 50 ° C.
From 300 ° C. to 300 ° C.

The products contained in the gas were analyzed using a gas chromatograph (GC-9A) manufactured by Shimadzu Corporation equipped with a column of Al ₂ O ₃ / KCl manufactured by Chrompack. Analysis conditions were as follows: using a nitrogen carrier, injection temperature 200 ° C., detector temperature 200 ° C., and column temperature 1
The temperature was set at 20 ° C., and the absolute calibration curve method was used. The analysis was performed by injecting 0.2 ml of the recovered gas into the gas chromatograph.

Reference Example 1 A Schlenk tube having an inner volume of 100 ml was placed in a J.L. Amer. C
hem. Soc. , 92, 5118 (1970). Tris (3,5-
126 mg of dimethyl-1-pyrazolyl) methane, tris (tetrahydrofuran) chromium trichloride (II
I) 143 mg and 20 ml of tetrahydrofuran were added,
The mixture was stirred under a nitrogen atmosphere for 12 hours. The generated crystals were separated by filtration to obtain tris (3,5-dimethyl-1-pyrazolyl) methanechrome trichloride (III) (hereinafter, referred to as complex A). REFERENCE EXAMPLE 2 12.8 g of naphthalene and 100 ml of ethylene glycol dimethyl ether were placed in a 200 ml Schlenk tube equipped with a magnetic rotator under a nitrogen atmosphere, 2.5 g of sodium metal was added, and the mixture was stirred at room temperature for 3 hours. 0.5 mol / l of generated sodium naphthalene
Titrated with a solution of 1-menthol in ethylene glycol dimethyl ether and found to be 1.0 mol / l.

Example 1 3.6 of the complex A synthesized in Reference Example 1 was placed in a 150-ml glass pressure-resistant reaction vessel equipped with a thermometer and a stirrer.
mg and 80 ml of dried toluene and 0.012 ml of a 1 mol / l solution of sodium naphthalene in ethylene glycol dimethyl ether were added and mixed and stirred.

The reaction vessel was heated to 80 ° C., and the stirring speed was 1
After adjusting to 100 rpm, 0.240 m by ethylene pressure
4.0 ml of an ol / l triisobutylaluminum / toluene solution were introduced to initiate the ethylene trimerization reaction. Ethylene gas was blown in so that the absolute pressure in the reaction vessel became 5 kg / cm ^2, and thereafter, introduction was continued so as to maintain the above-mentioned pressure.
The reaction was performed for 0 minutes. After 30 minutes, the catalyst was deactivated by forcing water into the reaction vessel with nitrogen and the reaction was stopped.

The reaction vessel was cooled to room temperature and then depressurized. No solid components such as polyethylene were found in the reaction solution. The products contained in the reaction solution and the recovered gas were analyzed by gas chromatography. Table 1 shows the results.

Example 2 2.4 m of triisobutylaluminum / toluene solution
The reaction was carried out in the same manner as in Example 1 except that 1 was added. Table 1 shows the results.

[0064]

[Table 1]

[0065]

According to the present invention, a trimerization catalyst for ethylene comprising a transition metal complex coordinated with a neutral polydentate ligand having a tripodal structure, an alkyl metal compound and a radical anion is stable and can be handled. And the use of this makes it possible to efficiently and highly selectively produce 1-hexene from ethylene.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 4/605 C08F 4/605 10/02 10/02 F term (Reference) 4G069 AA02 BA21A BA21B BA27A BA27B BC29A BC29B BC30A BC31A BC32A BC33A BC34A BC35A BC36A BC37A BC38A BC39A BC40A BC41A BC42A BC43A BC44A BC45A BC46A BC47A BC48A BC49A BC50A BC51A BC52A BC53A BC54A BC55A BC56A BC57A BC58A BC58B BC59A BC60A BC61A BC62A BC63A BC64A BC65A BC66A BC67A BC68A BC69A BC70A BC71A BC72A BC73A BC74A BC75A BD11A BD11B BD12A BD12B BD13A BD14A BD15A BD16A BE05A BE14A BE22A CB47 4H006 AC21 BA02 BA03 BA06 BA14 BA44 BA46 4H039 CA19 CF10 4H050 AB40 WB11 WB17 WB21 4J028 AA01A AB00A AB01A AC00A AC13A AC32A AC33ABCACB ACBBC AC41AACB ACBBC BC19B BC24B BC27B CB04C EB02 EB09 FA06 FA07

Claims (9)

[Claims] (1) LMX _n (1) wherein L is a neutral polydentate ligand having a tripod-type structure, and X is a halogen atom, an amide group, a sulfonyl group, an alkoxy group, Represents one or more selected from the group consisting of groups, M represents a transition metal of Groups 3 to 10 of the periodic table, and n is an integer equal to the oxidation number of the transition metal M.) An ethylene trimerization catalyst comprising a transition metal complex of Groups 3 to 10 of the periodic table coordinated with a neutral polydentate ligand, an alkyl metal compound and a radical anion. 2. The catalyst for trimerizing ethylene according to claim 1, wherein the transition metal is a Group 6 metal of the periodic table. 3. The ethylene trimerization catalyst according to claim 1, wherein the transition metal is chromium. 4. A neutral polydentate ligand having a tripod-type structure,
The following general formula (2) (In the formula, j, k, and m are each independently an integer of 0 to 6. D ¹ is each independently a divalent hydrocarbon group which may have a substituent, and L ¹ is Independently, it represents a substituent containing an element of group 14, 15, 15, 16 or 17. In addition, G ¹ is carbon or silicon, R ¹ is a hydrogen group, an alkyl group having 1 to 10 carbon atoms, or Carbon number 6-1
Represents an aryl group of 0. ) Or the following general formula (3): (In the formula, a, b, and c are each independently an integer of 0 to 6, and u is an integer of 0 or 1. D ² is each independently a 2 which may have a substituent. Valent hydrocarbon groups,
L ² each independently represent a periodic table group 14 group, group 15 group,
Represents a substituent containing a Group 13 or Group 17 element. G
² represents nitrogen or phosphorus, and R ² represents oxygen or sulfur. )
2. A tridentate ligand represented by the formula:
The catalyst for trimerizing ethylene according to claim 3. 5. A neutral polydentate ligand having a tripod-type structure,
The ethylene trimerization catalyst according to any one of claims 1 to 4, wherein a transition metal complex of Groups 3 to 10 of the periodic table coordinated with a factor is used. 6. An alkyl metal compound represented by the following general formula (4): R _p M′X _q (4) (where p is 0 <p ≦ 3, q is 0 ≦ q <3, And p + q is 1 to 3. M ′ represents lithium, sodium, potassium, magnesium, zinc, boron or aluminum, R represents one or more selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, X is a compound selected from the group consisting of a hydrogen atom, an alkoxy group, an amide group, an aryl group and a halogen atom.). Catalyst for trimerizing ethylene. 7. The radical anion represented by the following general formula (5): Ar ^{− ·} M ″ ⁺ (5) (wherein, Ar represents one or more selected from the following general formulas (6) to (8): Chemical formula 3] Embedded image Embedded image (Wherein, R 1 to R 28 each independently represent a hydrogen atom, a substituent containing a Group 13, 14, 15 or 16 element in the periodic table, and two adjacent substituents have a cyclic structure or an aromatic structure. Which may form a ring, including a hetero element-containing aromatic compound in which a carbon atom on the aromatic ring at the Ar site is substituted with a Group 15 element or a Group 16 element.) Represents one or more metals selected from alkali metals and alkaline earth metals. The ethylene trimerization catalyst according to any one of claims 1 to 6, which is a compound represented by the formula: 8. The method according to claim 1, wherein the radical anion is sodium naphthalene, sodium biphenyl, lithium (1- (N, N-
Dimethylamino) naphthalene), sodium (1-
(N, N-dimethylamino) naphthalene), potassium (1- (N, N-dimethylamino) naphthalene), lithium (4,4′-di (t-butyl) biphenyl), and magnesium anthracene. The ethylene trimerization catalyst according to claim 1, wherein the catalyst is at least one kind. 9. A method for trimerizing ethylene, wherein ethylene is trimerized in the presence of the ethylene trimerization catalyst according to any one of claims 1 to 8.