DE10054649A1 - New monocyclopentadienyl-alkyl-phosphido, -oxido, -amino and -sulfido compounds of group 3 to 8 transition metals are used as olefin polymerization catalyst components - Google Patents

Abstract

Monocyclopentadienyl-alkyl-phosphido, -oxido, -amino and -sulfido compounds (IA) of group 3 to 8 transition metals, with specified substituents, are new. New monocyclopentadienyl-alkyl-phosphido, -oxido, -amino- and -sulfido compounds (IA) of group 3 to 8 transition metals, with specified substituents, are represented by formula (I). Z = phosphorus (P), oxygen (O), nitrogen (N) or sulfur (S); M<4> = a group 3 to 8 element; R<2-5> = R or R' or together form a (substituted) cyclic system; R = hydrogen (H), 1-18 carbon (C) alkyl, 3-12 C cycloalkyl, 2-10 C alkenyl, 3-15 C alkylalkenyl, 6-18 C aryl, 5-18 C heteroaryl, 7-20 C arylalkyl or 7-20 C alkylaryl; R' = 1-12 C fluoroalkyl, 6-18 C fluoroaryl, 7-20 C fluoroarylalkyl or 7-20 C fluoroalkylaryl; R<6> = R; R<10> = H, halogen, 1-20 C hydrocarbyl, 6-20 C aryl, 6-20 C aryloxy or 1-20 C alkoxy; R<30> = R or R'; R<30> = are not identical groups if Z = N. Independent claims are also included for: (a) the preparation of compounds of formula (I) where R<10> = H, halogen, 1-18 C alkyl, 3-12 C cycloalkyl, 6-20 C aryl, 6-20 C aryloxy, 1-20 C alkoxy or a compound containing N; and R<30>= the same or different ligands. (b) catalysts containing cocatalyst(s), (I) and optionally support(s)

Description

The present invention relates to a method for manufacturing of special transition metal compounds, new transition metal compounds and their use for the polymerization of olefins.

Metallocenes can, optionally in combination with one or several co-catalysts, as a catalyst component for the Po Lymerization and copolymerization of olefins can be used. In particular, halogen-containing Me tallocenes used, for example, by an alumino xan in a polymerization-active cationic metallocene Have plex transferred.

The production and use of monocyclopentadienyl compounds gene is known per se and are for example in EP-A-0416815 and US 5026798. For example, cyclopenta dienyl metal compounds with halides or amides from Über transition metals such as titanium, zirconium and hafnium are implemented.

This "Constraind geometry" catalysts described there are particularly notable for their good copolymerization properties Based on ethylene and higher olefins.

By changing the bridge atoms between cyclopentadienylli ganden and coordination point on the metal atom can change who is achieved in activity and in copolymerization behavior the. For this purpose, several different bridges are known and z. B. in Organometallics 2000, 19, 2556-2563. This connection genes do not have the classic constraind geometry and are therefore not to be used for technical use.

In addition, the representation of these complexes runs over one more stage synthesis in sometimes poor yields, this leads directly at increased costs and thus only to a limited extent commercial use.

The task was therefore to create a new synthetic approach to find this class of compounds, which has the disadvantages of be avoids written prior art.  

It has now surprisingly been found that starting from sub substituted or unsubstituted fulvenes, amino fulves or ful vein structure analog systems provide universal access to the above described connection class is enabled and thus that of Invention underlying problem is solved.

The present invention relates to a process for the preparation of compounds of the formula (VII)

wherein
R ^{30 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl or octyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl such as phenyl, tolyl, xylyl, C ₅ -C ₁₈ heteroaryl such as furanyl, pyridinyl, C ₇ -C ₂₀ - Arylalkyl, C ₇ -C ₂₀ -alkylaryl, fluorine-containing C ₁ -C ₁₂ -alkyl, fluorine-containing C ₆ -C ₁₈ -aryl, fluorine-containing C ₇ -C ₂₀ -arylalkyl or fluorine-containing C ₇ -C ₂₀ -alkylaryl, preferably hydrogen, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₆ -C ₁₈ aryl, such as phenyl, tolyl xylyl, particularly preferably hydrogen, methyl Is ethyl, n-butyl, n-hexyl, tert-butyl, phenyl and tolyl, where the R ³⁰ ligands can be the same or different,
R ² , R ³ , R ⁴ , R ^{5, the} same or different, represent a hydrogen atom, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, isopropyl, isobutyl, cyclopentyl, C ₃ -C ₁₂ - Cycloalkyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, such as furanyl, pyridinyl, C ₇ -C ₂₀ arylalkyl , C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ alkylaryl, preferably C ₁ - C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl C ₆ -C ₁₈ aryl, such as phenyl tolyl xylyl, particularly preferably methyl, ethyl, n-butyl, is n-hexyl, tert-butyl, phenyl and tolyl, the radicals R ² , R ³ , R ⁴ and R ⁵ can form cyclic systems with one another, such as indenyls, benzindenyls, fluoreyl and phenanthryl, which in turn can in turn be substituted,
R ^{6 is} a hydrogen atom, a C ₁ -C ₂₀ carbon-containing group, preferably C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isobutyl, isopropyl, cyclopentyl, C ₃ -C ₁₂ -Cy cloalkyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkyl lalkenyl, C ₆ -C ₁₈ aryl, C ₆ -C ₁₈ aryl, such as phenyl, tolyl, xylyl , C ₅ -C ₁₈ heteroaryl, such as furanyl, pyridinyl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, preferably hydrogen, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, cyclohexyl C ₆ - Is C ₁₈ aryl, such as phenyl, tolyl,
R ^{10 is} a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ carbon group, such as methyl, ethyl, propyl, isopropyl, isobutyl, a C ₅ -C ₂₀ aryl, such as phenyl, tolyl, xylyl, a C ₅ -C ₂₀ aryloxy - Group, such as substituted or unsubstituted phenoxy and biphenoxy, a C ₁ -C ₂₀ alkyloxy group, a nitrogen-containing compound, preferably fluorine and chlorine, methyl, ethyl, phenyl, substituted or unsubstituted phenoxy, NMe ₂ , NEt ₂ , very particularly preferably chlorine, NMe ₂ , NEt ₂ ,
Z is phosphorus, oxygen, nitrogen and sulfur, particularly preferably phosphorus,
M ^{4 is} an element from the 3rd to 10th group of the Periodic Table of the Elements, particularly preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, very particularly preferably titanium, zirconium and hafnium,
comprehensively the steps

• A) implementation of a compound of formula I.
  wherein,
  R ^{1 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₃ -C ₁₂ cycloal kyl, cyclopentyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₆ -C ₁₈ aryl such as phenyl, tolyl, xylyl, C ₅ -C ₁₈ heteroaryl such as furanyl, Pyridinyl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ -alkylaryl, preferably C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₆ -C ₁₈ -aryl, such as phenyl, tolyl xylyl, is particularly preferably methyl, ethyl, n-butyl, n-hexyl, tert-butyl, phenyl and tolyl and R ² , R ³ , R ⁴ , R ^{5 have} the meaning given under formula (VII),
  X oxygen, nitrogen and sulfur, particularly preferably nitrogen,
  y is 1 or 2,
  with a compound of formula (II),
  M ¹ R ⁶ ZR ⁷ (II)
  wherein
  Z and R ^{6 have} the meaning given under formula (VII),
  M ^{1 is} an element of the 1st or 2nd group of the Periodic Table of the Elements, preferably lithium, sodium, potassium and magnesium, particularly preferably lithium,
  R ^{7 is} a hydrogen atom, C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₃ -C ₁₂ -cycloal kyl, cyclopentyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₆ -C ₁₈ aryl such as phenyl, tolyl, xylyl, C ₅ -C ₁₈ heteroaryl such as furanyl , Pyridinyl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ - C ₂₀ alkylaryl is, preferably hydrogen, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₆ -C ₁₈ aryl, such as phenyl Tolyl xylyl, particularly preferably hydrogen, methyl, ethyl, n-butyl, n-hexyl, tert-butyl, phenyl and tolyl,
  to a compound of formula (III)
  wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ³⁰ , Z, M ¹ and y have the meanings described above
• B) reaction of the compound of formula (III) obtained in step A) with an organometallic compound of the formula IV
  M ² R ⁸ (IV)
  wherein
  M ^{2 is} an element of the 1st or 2nd group of the Periodic Table of the Elements, preferably lithium, sodium, potassium and magnesium, particularly preferably lithium,
  R ⁸ preferably represents a hydrogen atom, C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, sec-butyl, particularly preferably methyl, n-butyl, sec-butyl, to a compound of formula (V)
  wherein
  R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ³⁰ , Z and y have the meaning described above and
  M ^{3 is} an element of the 1st or 2nd group of the Periodic Table of the Elements, preferably lithium, sodium, potassium and magnesium, particularly preferably lithium and has the same meaning as M ¹ or M ² ,
• C) reaction of the compound of formula (V) obtained in step B) with a compound of the formula (VI)
  M ⁴ (R ⁹ ) _f (R ¹⁰ ) _g (R ¹¹ ) _k (VI)
  wherein
  M ^{4 is} an element of the 3rd to 8th group of the Periodic Table of the Elements, particularly preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, very particularly preferably titanium, zirconium and hafnium,
  R ^{9 is} a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ carbon group, such as methyl, ethyl, propyl, isopropyl, a C ₅ -C ₂₀ aryl, such as phenyl, tolyl, xylyl, a C ₅ -C ₂₀ aryloxy- Group, such as substituted or unsubstituted phenoxy and biphenoxy, preferably fluorine and chlorine, methyl, ethyl, phenyl, substituted or unsubstituted phenoxy, very particularly preferably chlorine, methyl, phenyl,
  R ^{10 is} a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ carbon group, such as methyl, ethyl, propyl, isopropyl, isobutyl, a C ₅ -C ₂₀ aryl, such as phenyl, tolyl, xylyl, a C ₅ -C ₂₀ aryloxy A group such as substituted or unsubstituted phenoxy and biphenoxy, a nitrogen-containing radical, preferably fluorine and chlorine, methyl, ethyl, phenyl, substituted or unsubstituted phenoxy, NMe ₂ , NEt ₂ , very particularly preferably chlorine, NMe ₂ , NEt ₂ ,
  R ^{11 is} C ₁ -C ₂₀ heterocarbon compound, preferably a C ₁ -C ₂₀ heterocarbon group, linear or cyclic or aromatic ethers, thiols, such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, diisopropyl ether, di-n-butyl ether, tetrahydrofuran , Tetrahydrothiophene, very particularly preferably diethyl ether and tetrahydrofuran.
  f is a number from 1-10, preferably 1-6, very preferably 2,
  g is a number from 1-10, preferably 1-6, very preferably 2,
  k is a number from 1-10, preferably 1-6, very preferably 2,
  to the compound of general formula (VII) according to the invention.

First, a compound of formula (I) in one reaction be submitted to vessel. The connections can either be in one Solvent can be dissolved or suspended, or in sub punch available. Aliphatic or aromatic solvents are used hydrocarbons such as n-pentane, isopentane, n-hexane, n-Hep tan, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethyl benzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-tri methylbenzene, ethylbenzene, propylbenzene etc. and ethers such as Diethyl ether, methyl tert-butyl ether, dimethoxyethane, diisopropy ether, di-n-butyl ether, anisole or mixtures thereof. The Submission takes place at temperatures between -100 ° C and 300 ° C before moves between -80 ° C and 200 ° C, particularly preferred at tempera doors between 20 ° C and 150 ° C. The compound of formula (I) should advantageously be in the liquid phase.

Then he can follow the addition of a compound of formula (II). These can also be dissolved or suspended in a solvent, but can also be in bulk. The solvents already described above are used as solvents, preferably the same solvent is used. The addition can take place over a period of 1 minute to 96 hours. An addition within 10 minutes to 8 hours is preferred. The temperature of the template is generally between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 150 ° C are preferred. Temperatures between 20 ° C and 150 ° C are particularly preferred. The temperature is generally chosen so that at least one reaction partner is in the liquid phase. The subsequent reaction temperature is generally in a preferred temperature range between 20 ° C and 150 ° C. Furthermore, the implementation can be carried out at normal pressure, but it can also be carried out at elevated pressure, but this requires appropriate reactors. The molar ratio in which compounds of the formula (I) and (II) are combined, based on a set amount M ^{1 of} the compounds of the formula (I), is between 1: 1000 and 1: 0.01. A ratio between compounds of formula (I) and (II) to the amount of M ^{1 used} , according to formula (I), between 1: 100 and 1: 0.1 is preferred. A stoichiometric conversion based on the compounds of the formula (I) and (II) is particularly preferred.

The compounds of formula II can be used in pure substance or in situ from a base such as lithium diisopropylamide and one Amine can be generated. Non-limiting examples of the be preferred compounds of formula (II) are: lithium phosphide, Li thiumcyclohexylphosphid, Lithiumcyclopentylphosphid, Lithiumphe nylphospid, Lithium-methylphospid, Lithiumtertbutylphospid, Li thium-2,6- (diisopropyl) phenylphosphide, lithium ethylphosphide, Li thium isopropyl phosphide, lithium 2,6- (ditert.butyl) phenyl phosphide, Lithium 2,6- (dimethyl) phenylphosphide, Lithium 2,6- (diethyl) phe nylphospid, lithium 3-methylphenylphosphid, lithium 3-ethylphenyl phospid, lithium 2,5- (diisopropyl) phenylphosphide, Li thium-4-ethylphenylphosphid, lithium 4-isopropylphenylphosphid, Li thium-2,5- (ditert.butyl) phenylphosphide, lithium-2,5- (dime thyl) phenylphosphide, lithium 2,5- (diethyl) phenylphosphide, Li thium-2,3- (diisopropyl) phenylphosphide, lithium-2,3- (ditert.bu tyl) phenylphosphide, lithium 2,3- (dimethyl) phenylphosphide, Li thium-2,3- (diethyl) phenylphosphide, lithium-2,4- (diisopropyl) phe nylphospid, lithium 2,4- (ditert.butyl) phenylphospid, lithium-2, 4- (dimethyl) phenylphosphide, lithium 2,4- (diethyl) phenylphosphide, Sodium phenylphosphide, sodium 4-methylphenylphosphide, sodium tert butylphenyl phosphide, sodium tert-butyl phosphide, sodium 2,6- (dii sopropyl) phenylphosphide, sodium 4-ethylphenylphosphide, Na trium-4-isopropylphenylphosphide, sodium 2,6- (ditert.butyl) phe nylphosphide, sodium 2,6- (dimethyl) phenylphosphide, sodium 2, 6- (diethyl) phenylphosphide, sodium 3-methylphenylphosphide, Na trium-3-ethylphenylphosphide, sodium 2,5- (diisopropyl) phenylphos pid, sodium 4-ethylphenylphosphide, sodium 4-isopropylphenylphos pid, sodium 2,5- (ditert.butyl) phenylphosphide, sodium 2,5- (di methyl) phenylphosphide, sodium 2,5- (diethyl) phenylphosphide, Na trium-2,3- (diisopropyl) phenylphosphide, sodium 4-ethylphenylphos pid, sodium 4-isopropylphenylphosphide, sodium 2,3- (ditert.bu tyl) phenylphosphide, sodium 2,3- (dimethyl) phenylphosphide, Na trium-2,3- (diethyl) phenylphosphide, sodium 2,4- (diisopropyl) phe nylphospid, sodium 4-ethylphenylphosphid, sodium isopropylphos pid, sodium 2,4- (ditert.butyl) phenylphosphide, sodium 2,4- (di methyl) phenylphosphide, sodium 2,4- (diethyl) phenylphosphide, potash umphenylphosphide, potassium methylphosphide, potassium tert-butylphenylphos pid, potassium tert-butyl phosphide, potassium 2,6- (diisopropyl) phenyl phospid, potassium 4-ethylphenylphosphid, potassium 4-isopropylphenyl phospid, potassium 2,6- (ditert.butyl) phenylphosphide, potassium-2, 6- (dimethyl) phenylphosphide, potassium 2,6- (diethyl) phenylphosphide, Potassium 3-methylphenylphosphide, potassium 3-ethylphenylphosphide, Ka lium-2,5- (diisopropyl) phenylphosphide, potassium 4-ethylphenylphos pid, potassium 4-isopropylphenylphosphide, potassium 2,5- (ditert.bu tyl) phenylphosphide, potassium 2,5- (dimethyl) phenylphosphide, potassium 2, 5- (diethyl) phenylphosphide, potassium 2,3- (diisopropyl) phenylphosphide, Potassium 4-ethylphenylphosphide, potassium 4-isopropylphenylphosphide, Ka  lium-2,3- (ditert.butyl) phenylphosphide, potassium-2,3- (dimethyl) phe nylphosphide, potassium 2,3- (diethyl) phenylphosphide, potassium 2,4- (dii sopropyl) phenylphosphide, potassium 4-ethylphenylphosphide, Ka lium-4-isopropylphenylphosphide, potassium 2,4- (ditert.butyl) phenyl phosphid, potassium 2,4- (dimethyl) phenylphosphide, potassium 2,4- (the thyl) phenylphospid.

In the next step, one or more connections of the For mel (III) are placed in a reaction vessel. The verb solutions can either be dissolved in a solvent or suspended be dated, or also be in substance. As a solvent serve aliphatic or aromatic hydrocarbons such as n- Pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, Pro pylbenzene etc. and ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, diisopropyl ether, di-n-butyl ether, anisole or mixtures of these. It is usually submitted to Temperatures between -100 ° C and 300 ° C, preferably between -80 ° C and 200 ° C, particularly preferably at temperatures between 20 ° C and 150 ° C. The compound of formula (III) should be more advantageous wise in the liquid phase.

Then one or more compounds of the formula (TI) can be added. These can also be dissolved or suspended in a solvent, but can also be in bulk. The solvents already described above are used as solvents, preferably the same solvent is used. The addition can take place over a period of 1 minute to 96 hours. An addition within 10 minutes to 8 hours is preferred. The temperature of the template is usually between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 150 ° C are preferred. Temperatures between 20 ° C and 150 ° C are particularly preferred. The temperature is generally chosen so that at least one reactant is in the liquid phase. The subsequent reaction temperature is usually in a preferred temperature range between 20 ° C and 150 ° C. Furthermore, the reaction can be carried out at normal pressure, but it can also be carried out at elevated pressure, but this requires appropriate reactors. The ratio in which compounds of formula (III) and (IV) are combined, based on the amount M ² of compounds of formula (IV) used, is generally between 1: 1000 and 1: 0.01. A molar ratio between compounds of the formula (III) and (IV) to the amount of M ^{2 used} , according to formula (IV), between 1: 100 and 1: 0.1 is preferred.

A stoichiometric conversion is particularly preferred to the compounds of formula (III) and (IV).

The compound V can be isolated or presented in situ and vice versa be set.

In a variant of the process according to the invention, the compound of the formula V is converted by reacting the compound of the formula VIII (instead of the compound of the formula I)

wherein,
R ^{30 has} the meaning given above,
R ^{20 is} a hydrogen atom, C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₃ -C ₁₂ -cycloal kyl, cyclopentyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₆ -C ₁₈ aryl such as phenyl, tolyl, xylyl, C ₅ -C ₁₈ heteroaryl such as furanyl , Pyridinyl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ - C ₂₀ alkylaryl is, preferably hydrogen, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₆ -C ₁₈ aryl, such as phenyl , Tolyl Xy lyl, particularly preferably hydrogen, methyl, ethyl, n-butyl, n-hexyl, tert-butyl, phenyl and tolyl and R ² , R ³ , R ⁴ , R ^{5 has} the meaning given under formula (VII) to have,
with a compound of formula (II),

M ¹ R ⁶ ZR ⁷ (II)

wherein
Z, R ⁶ , M ¹ and R ^{7 have} the meanings listed above,
to a compound of formula (IX)

wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ²⁰ , R ³⁰ , Z, M ^{1 have} the meanings described above and
R ^{21 is} a hydrogen atom, C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₃ -C ₁₂ -cycloal kyl, cyclopentyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₆ -C ₁₈ aryl such as phenyl, tolyl, xylyl, C ₅ -C ₁₈ heteroaryl such as furanyl , Pyridinyl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ - C ₂₀ -alkylaryl is, preferably C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₆ -C ₁₈ -aryl, such as phenyl, tolyl xylyl is particularly preferably methyl, ethyl, n-butyl, n-hexyl, tert-butyl, phenyl and tolyl,
and subsequent reaction of the compound of formula IX with an organometallic compound of formula X.

M ⁵ R ²² (X)

wherein
M ^{2 is} an element of the 1st or 2nd group of the Periodic Table of the Elements, preferably lithium, sodium, potassium and magnesium, particularly preferably lithium.
R ²² C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, sec-butyl, particularly preferably methyl, n-butyl, sec-butyl, or an N (R ⁵⁰ ) _p unit in the R ⁵⁰ preferably C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, sec-butyl, isopropyl, particularly preferably methyl, ethyl , is tert-butyl or isopropyl, and p = 2,
to the compound of formula V described above

The compounds of formula X can be used in pure substance or generated in situ. Nonlimiting examples of the preferred compounds of formula (X) are:
Lithium diisopropylamide, lithium dimethylamide, lithium diethylamide, lithium diphenylamide, lithium dicyclohexylamide, Lithiumdibenzylamid, Lithiumisopropylmethylamid, Lithiumdibutylamid, Lithiumditert.butylamid, Lithiumditolylamid, Lithiumdicyclopentylamid, Lithiumdibutylamid, Lithiummethylethylamid, Lithiumethylbutylamid, sodium diisopropylamide, Natriumdimethylamid, sodium diethylamide, Natriumdiphenylamid, Natriumdicyclohexylamid, Natriumdibenzylamid, Natriumisopropylmethylamid, Natriumdibutylamid, Natriumditert.butylamid, Natriumditolylamid, Natriumdicyclopentylamid, Natriumdibutylamid, Natriummethylethylamid, Natriumethylbutylamid, potassium diisopropylamide, Kaliumdimethylamid, Kaliumdiethylamid, Kaliumdiphenylamid, Kaliumdicyclohexylamid, Kaliumdibenzylamid, Kaliumisopropylmethylamid, Kaliumdibutylamid, Kaliumditert.butylamid, Kaliumditolylamid, Kaliumdicyclopentylamid, Kaliumdibutylamid, Kaliummethylethylamid and / or Kaliummethylbutylamid.

The reaction conditions as well as stoichiometric ratios for the variant of the method according to the invention for the production of Compound V are analogous to those described above for the implementation tongues of compounds of formula I with compounds of formula II and for the reactions of the compounds of formula III with the compound of formula IV.

In the next step, one or more connections of the For mel (V) are placed in a reaction vessel. The connection gene can either be dissolved or suspended in a solvent be, or also be in substance. Serve as a solvent usually aliphatic or aromatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, Pro pylbenzene etc. and ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, diisopropyl ether, di-n-butyl ether, anisole or mixtures of these. It is usually submitted to Temperatures between -100 ° C and 300 ° C, preferably between -80 ° C and 200 ° C, particularly preferably at temperatures between 20 ° C and 150 ° C. The compound of formula (V) should advantageously are in the liquid phase.

One or more compounds of the formula (VI) can then be added. These can also be dissolved or suspended in a solvent, but can also be in bulk. The solvents already described above are used as solvents, preferably the same solvent is used. The addition can take place over a period of 1 minute to 96 hours. An addition within 10 minutes to 8 hours is preferred. The temperature of the template is usually between -100 ° C and 200 ° C when added. Temperatures between -80 ° C and 150 ° C are preferred. Temperatures between 20 ° C and 150 ° C are particularly preferred. The temperature is chosen so that at least one reactant is present in the liquid phase. The subsequent reaction temperature is in a preferred temperature range between 20 ° C and 150 ° C. Furthermore, the reaction can be carried out at normal pressure, but it can also be carried out at elevated pressure, which, however, requires appropriate reactors. The ratio in which compounds of the formula (V) and (VI) are combined, based on the amount of M ^{3 used for} the compounds of the formula (V), is between 1: 1000 and 1: 0.01. A stoichiometric ratio between compounds of the formula (V) and (VI) to the amount of M ^{3 used} , according to formula (VI), is between 1: 100 and 1: 0.1. A stoichiometric conversion based on the compounds of the formulas (V) and (VI) is particularly preferred.

The present invention also relates to a chemical compound of the formula (VII-A) according to the invention

wherein
R ^{30 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₃ - C ₁₂ cycloalkyl, cyclopentyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₆ -C ₁₈ aryl such as phenyl, tolyl, xylyl, C ₅ -C ₁₈ heteroaryl such as furanyl, pyridinyl , C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylla ryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ - Is C ₂₀ alkylaryl, preferably hydrogen, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl, C ₆ -C ₁₈ aryl, such as phenyl, To lyl, xylyl, particularly preferably hydrogen, methyl, ethyl, n-butyl, n-hexyl, tert-butyl, phenyl and tolyl, where for Z = nitrogen the R ³⁰ substituents do not have the same meaning together, and for Z = phosphorus the R ³⁰ substituents together can have the same meaning,
R ² , R ³ , R ⁴ , R ^{5, the} same or different, represent a hydrogen atom, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, isopropyl, isobutyl, C ₃ -C ₁₂ cycloalkyl, Cyclopentyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, such as furanyl, pyridinyl, C ₇ -C ₂₀ - Arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ alkylaryl, preferably C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl C ₆ -C ₁₈ aryl, such as phenyl tolyl xylyl, particularly preferably methyl, ethyl, n-butyl is n-hexyl, tert-butyl, phenyl and tolyl, the radicals R ² , R ³ , R ⁴ and R ⁵ can form cyclic systems with one another, such as indenyls, benzindenyls, fluoreyl and phenanthryl, which in turn can in turn be substituted .
R ^6, identical or different, is a hydrogen atom, C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-butyl, n-hexyl, isopropyl, isobutyl, C ₃ -C ₁₂ cycloalkyl, cyclopentyl, cyclohexyl or octyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, such as furanyl, pyridinyl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ - Is alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ alkylaryl, preferably C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, isopropyl, isobutyl C ₆ -C ₁₈ aryl, such as phenyl tolyl xylyl, particularly preferably methyl, ethyl cyclohexyl, n-butyl, n-hexyl, tert . -Butyl, phenyl and tolyl,
R ^{10 is} a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ carbon group such as methyl, ethyl, propyl, isopropyl, isobutyl, a C ₅ -C ₂₀ aryl such as phenyl, tolyl, xylyl, a C ₆ -C ₂₀ Aryloxy group, such as substituted or unsubstituted phenoxy and biphenoxy, a C ₁ -C ₂₀ alkyloxy group, a nitrogen-containing compound, preferably fluorine and chlorine, methyl, ethyl, phenyl, substituted or unsubstituted phenoxy, NMe ₂ , NEt ₂ , is very particularly preferably chlorine, NMe ₂ , NEt ₂ ,
Z is phosphorus, oxygen, nitrogen and sulfur, particularly preferably phosphorus,
M ^{4 is} an element 3 to 8 group of the elements of the periodic table, particularly preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, very particularly preferably titanium, zirconium and hafnium.

The dichloro and diamido compounds can be literally regulations on the corresponding butadiene (EP-A-0687682) or bisphenol complexes (DE-A-199 00 732) are implemented.

Non-limiting examples of the compound of formula VII or (VII-A) according to the invention are:
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} titanium
Bis (dimethylamido) {η ⁵ : κP-1- (P-cyclohexylphosphido) 2,2 methylpropylene-cyclopenta-dienyl} titanium
Bis (dimethylamido) {η ⁵ : κP-1- (P-cyclohexylphosphido) 1-methylethylidene-cyclopentadienyl} titanium
Bis (dimethylamido) {η ⁵ : κP-1- (P-cyclohexylphosphido) 1-methylethylidene-cyclopentadienyl} zirconium
Bis (diethylamido) (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopentadienyl) zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidency clopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tertbutylphospido) 2,2 methylpropylidene cyclopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κN- (P-tertbutylphospido) methyli den-2,3,4,5-tetramethylcyclopentadienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene-2,3,4,5-tetramethylcyclopentadienyl} titanium
Bischloro {η ⁵ : κP-1- (P-phenylphospido) ethylidene-2,3,4,5-tetrame thylcyclopentadienyl) zirconium
Bischloro (η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidene-2,3,4,5-th tramethylcyclopentadienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene-2,3,4,5-tetramethylcyclopentadienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-tertbutylphosphido) 2,2 methylpropylidene-2,3,4,5-tetramethylcyclopentadienyl} zirconium
Bischloro {η ⁵ : κN- (P-tertbutylphosphido) methylidene-2,3,4,5-tetrame thylcyclopentadienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopen tadienyl} titanium
Bischloro (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopentadiene nyl) zirconium
Bischloro {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidene cyclopenta dienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopen tadienyl) zirconium
Bischloro {η ⁵ : κP-1- (P-tertbutylphosphido) 2,2 methylpropylidene cyclo pentadienyl} zirconium
Bischloro {η ⁵ : κP- (P-tertbutylphosphido) methylidene-2,3,4,5-tetrame thylcyclopentadienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphosphido) 2,2 methylpropylidency clopentadienyl} titanium
Bischloro (η ⁵ : κP-1- (P-cyclohexylphospido) ethylidene cyclopentadiene nyl) zirconium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphospido) -p-tolylmethylidene cyclo pentadienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphosphido) 2,2 methylpropylidency clopentadienyl} zirconium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphospido) 2,2 methylpropylidene cyclo pentadienyl} zirconium
Bischloro {η ⁵ : κP- (P-cyclohexylphospido) methylidene-2,3,4,5-tetrame thylcyclopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κP-2- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} titanium
Bis (dimethylamido) (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopen tadienyl) zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidency clopentadienyl} zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tertbutylphospido) 2,2 methylpropylidene cyclopentadienyl} zirconium
Bis (dimethylamido) {η ⁵ : κP- (P-tertbutylphosphido) methyli-2,3,4,5-tetramethylcyclopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} hafnium
Bis (dimethylamido) (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopen tadienyl) hafnium
Bis (dimethylamido) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidency clopentadienyl} hafnium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} hafnium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tertbutylphospido) 2,2 methylpropylidene cyclopentadienyl} hafnium
Bis (dimethylamido) {η ⁵ : κN- (P-tertbutylphospido) methyli-2,3,4,5-tetramethylcyclopentadienyl} hafnium
Bischloro {η ⁵ : κN- (P-tertbutylphosphido) methylidene-2,3,4,5-tetrame thylcyclopentadienyl} hafnium
Bischloro {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopen tadienyl} hafnium
Bischloro (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopentadiene nyl) hafnium
Bischloro {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidene cyclopenta dienyl} hafnium
Bischloro {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopen tadienyl} hafnium
Bischloro {η ⁵ : κP-1- (P-tertbutylphosphido) 2,2 methylpropylidene cyclo pentadienyl} hafnium
Bischloro {η ⁵ : κP- (P-tertbutylphosphidomethyl-2,3,4,5-tetramethylcy clopentadienyl} hafnium
Bis (dimethylamido) {η ⁵ : κP-1- (P-cyclohexylphospido) 2,2 methylpropylidenecyclopentadienyl} hafnium
Bis (dimethylamido) {η ⁵ : κN- (P-cyclohexylphospido) methyli den-2,3,4,5-tetramethylcyclopen-tadienyl} hafnium
Bischloro {η ⁵ : κN- (P-cyclohexylphospido) methylidene-2,3,4,5-tetrame thylcyclopentadienyl} hafnium
Bischloro {η ⁵ : κP-2- (P-cyclohexylphosphido) 2,2 methylpropylidency clopentadienyl} hafnium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphospido) ethylidene cyclopentadiene nyl) hafnium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphospido) -p-tolylmethylidene cyclo pentadienyl} hafnium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphosphido) 2,2 methylpropylidency clopentadienyl} hafnium
Bischloro {η ⁵ : κP-1- (P-cyclohexylphospido) 2,2 methylpropylidene cyclo pentadienyl} hafnium
Bischloro {η ⁵ : κP- (P-cyclohexylphospido) methylidene-2,3,4,5-tetrame thylcyclopentadienyl} hafnium
(cis-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} titanium
(cis-η ⁴ -butadiene) (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopen tadienyl) zirconium
(cis-η ₄ -butadiene) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidency clopentadienyl} zirconium
(cis-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} zirconium
(cis-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tertbutylphospido) 2,2 methylpropylidene cyclopentadienyl} zirconium
(cis-η ⁴ -butadiene) {η ⁵ : κN- (P-tertbutylphospido) methyli-2,3,4,5-tetramethylcyclopen-tadienyl} zirconium
(cis-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} hafnium
(cis-η ⁴ -butadiene) (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopen tadienyl) hafnium
(cis-η ⁴ -butadiene) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidency clopentadienyl} hafnium
(cis-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} hafnium
(cis-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tertbutylphosphido) 2,2 methylpropylidene cyclopentadienyl} hafnium
(cis-η ⁴ -butadiene) {η ⁵ : κN- (P-tertbutylphosphido) methyli-2,3,4,5-tetramethylcyclopentadienyl} hafnium
(trans-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tolylphosphido) 2.2 methylpropylidene cyclopentadienyl} titanium
(trans-η ⁴ -butadiene) (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopentadienyl) zirconium
(trans-η ⁴ -butadiene) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidene cyclopentadienyl} zirconium
(trans-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tolylphosphido) 2.2 methylpropylidene cyclopentadienyl} zirconium
(trans-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tertbutylphospido) 2.2 methylpropylidenecyclopentadienyl} zirconium
(trans-η ⁴ -butadiene) {η ⁵ : κN- (P-tert-butylphosphido) methyli-2,3,4,5-tetramethylcyclopen-tadienyl} zirconium
(trans-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} hafnium
(trans-η ⁴ -butadiene) (η ⁵ : κP-1- (P-phenylphospido) ethylidene cyclopentadienyl) hafnium
(trans-η ⁴ -butadiene) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidene cyclopentadienyl} hafnium
(trans-η ⁴ -butadiene) {η ⁵ : κPP-1- (P-tolylphosphido) 2,2 methylpropylidene cyclopentadienyl} hafnium
(trans-η ⁴ -butadiene) {η ⁵ : κP-1- (P-tertbutylphosphido) 2,2 methylpropylidenecyclopentadienyl} hafnium
(trans-η ⁴ -butadiene) {η ⁵ : κN- (P-tertbutylphosphido) methyli-2,3,4,5-tetramethylcyclopentadienyl} hafnium
Bis (phenolato) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidency clopentadienyl} titanium
Bis (phenolato) (η ⁵ : κP-1- (P-phenylphospido) ethylcyclopentadienyl) zirconium
Bis (phenolato) {η ⁵ : κP-1- (P-phenylphospido) -p-tolylmethylidene cyclopentadienyl} zirconium
Bis (phenolato) {η ⁵ : κP-1- (P-tolylphosphido) 2,2 methylpropylidency clopentadienyl} zirconium
Bis (phenolato) {η ⁵ : κP-1- (P-tertbutylphospido) 2,2 methylpropylidene cyclopentadienyl} zirconium
Bis (phenolato) {η ⁵ : κN- (P-tertbutylphosphido) methylidene-2,3,4,5-th tramethylcyclopentadienyl} zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) isopropylmethylidene cyclopentadienyl} titanium
Bis (diethylamido) (η ⁵ : κP-1- (P-tolylphosphido) ethylidene cyclopenta dienyl) zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-phenylphospido) ethylmethylidene cyclopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tolylphosphido) cyclohexylmethylidene cyclopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tertbutylphospido) cyclohexylmethylidecyclopentadienyl} zirconium
Bis (diethylamido) {η ⁵ : κN- (P-tertbutylphospido) 2,2 methylpropylidene-2,3,4,5-tetramethylcyclopentadienyl} zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) isopropylmethylide nindenyl} titanium
Bis (diethylamido) (η ⁵ : κP-1- (P-tolylphosphido) ethylindenyl) zirco nium
Bis (diethylamido) {η ⁵ : κP-1- (P-phenylphospido) ethylmethylideninde nyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tolylphosphido) cyclohexylmethylide nindenyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tertbutylphosphido) cyclohexylmethylidindenyl} zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) isopropylmethylidene benzindenyl} titanium
Bis (diethylamido) (η ⁵ : κP-1- (P-tolylphosphido) ethylidene benzene nyl) zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-phenylphospido) ethylmethylidenbenzindenyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tolylphosphido) cyclohexylmethylidene benzindenyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tertbutylphospido) cyclohexylmethylidbenzindenyl} zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) isopropylmethylidene fluorenyl} titanium
Bis (diethylamido) (η ⁵ : κP-1- (P-tolylphosphido) ethylfluorenyl) zir conium
Bis (diethylamido) {η ⁵ : κP-1- (P-phenylphospido) ethylmethylidene fluoro renyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tolylphosphido) cyclohexylmethylidene fluorenyl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tert-butylphosphido) cyclohexylmethylidefluorenyll-zirconium
Bis (dimethylamido) {η ⁵ : κP-1- (P-tolylphosphido) isopropylmethylidene phenantryl} titanium
Bis (diethylamido) (η ⁵ : κP-1- (P-tolylphosphido) ethylidene phenane tryl) zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-phenylphospido) -ethylmethylidenphe nantryl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tolylphosphido) cyclohexylmethylidene phenantryl} zirconium
Bis (diethylamido) {η ⁵ : κP-1- (P-tertbutylphospido) cyclohexylmethylidphenantryl} zirconium.

The present invention also relates to a catalyst system which the chemical compound of the formula VII contains.

The metal complexes of the formulas VII according to the invention are suitable especially as a component of catalyst systems for the manufacture treatment of polyolefins by polymerizing at least one Olefin in the presence of a catalyst which has at least one Co contains catalyst and at least one metal complex.

The cocatalyst, which together with an over invention gear metal complex of the formulas VII forms the catalyst system, contains at least one compound of the aluminoxane type or a Lewis acid or an ionic compound, which is represented by Re action with a metallocene into a cationic compound transferred.

A compound of the general formula (XI) is preferred as the aluminoxane

(R AlO) _n (XI)

used.

Other suitable aluminoxanes can e.g. B. cyclic as in formula (XII)

or linear as in formula (XIII)

or of the cluster type as in formula (XIV)

his. Such aluminoxanes are described, for example, in JACS 117 (1995), 6465-74, Organometallics 13 (1994), 2957-2969 ben.

The radicals R in the formulas (XI), (XII), (XIII) and (XIV) can be identical or different and have a C ₁ -C ₂₀ hydrocarbon group such as a C ₁ -C ₆ alkyl group, a C ₆ - C ₁₈ aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.

The radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.

If the radicals R are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl where in the case of hydrogen or isobutyl or n-butyl, preferably 0.01-40% (Number of residues R) are included.

The aluminoxane can be prepared in various ways according to known procedures be manufactured. For example, one of the methods is that an aluminum hydrocarbon compound and / or a hydri doaluminium hydrocarbon compound with water (gaseous, solid, liquid or bound - for example as crystal water) in an inert solvent (such as toluene).  

To produce an aluminoxane with different alkyl groups R, two different aluminum trialkyls (AIR ₃ + AIR ' ₃ ) are reacted with water according to the desired composition and reactivity (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0,302,424 ).

All aluminoxane solutions are independent of the type of production a changing content of unreacted aluminum gangsverbindung, which is in free form or as an adduct, ge Together.

As Lewis acid preferably at least one organic boron or alumi nium compound are used which contain C ₁ -C ₂₀ carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as. B. methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di (trifluoromethyl) phenyl.

Examples of Lewis acids are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, trifluoroborane, triphenylborane,
Tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyl) borane, tris ( 3,5-difluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.

As ionic cocatalysts, preference is given to using compounds which contain a non-coordinating anion, such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF ₆ ^- , CF ₃ SO ₃ ^- or ClO ₄ ^- . Protonated Lewis bases such as, for. B. methylamine, aniline, N, N-dimethylbenzylamine and derivatives, N, N-dimethylcyclohexylamine and derivatives, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, Methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene or triphenylcarbenium is used.

Examples of such ionic compounds are
Triethylammonium tetra (phenyl) borate,
Tributylammoniumtetra (phenyl) borate,
Trimethylammoniumtetra (tolyl) borate,
Tributylammoniumtetra (tolyl) borate,
Tributylammonium tetra (pentafluorophenyl) borate,
Tributylammonium tetra (pentafluorophenyl) aluminate,
Tripropylammoniumtetra (dimethylphenyl) borate,
Tributylammoniumtetra (trifluoromethylphenyl) borate,
Tributylammoniumtetra (4-fluorophenyl) borate,
N, N-dimethylanilinium tetra (phenyl) borate,
N, N-diethylaniliniumtetra (phenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate,
Di (propyl) ammoniumtetrakis (pentafluorophenyl) borate,
Di (cyclohexyl) ammoniumtetrakis (pentafluorophenyl) borate,
Triphenylphosphonium tetrakis (phenyl) borate,
Triethylphosphoniumtetrakis (phenyl) borate,
N, N-Dimethylcyclohexylammoniumtetrakis (pentafluorophenyl) borate,
N, N-Dimethylbenzylammoniumtetrakis (pentafluorophenyl) borate,
Diphenylphosphoniumtetrakis (phenyl) borate,
Tri (methylphenyl) phosphoniumtetrakis (phenyl) borate,
Tri (dimethylphenyl) phosphoniumtetrakis (phenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,
Triphenylcarbenium tetrakis (phenyl) aluminate,
Ferrocenium tetrakis (pentafluorophenyl) borate and / or
Ferrocenium (pentafluorophenyl) aluminate.

Triphenylcarbenium tetrakis (pentafluorophenyl) borate are preferred and or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

Mixtures of at least one Lewis acid and at least one least an ionic compound can be used.

As cocatalyst components are also borane or carborane compounds such. B.
7,8-dicarbaundecaborane (13),
Undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,
Dodecahydride-1-phenyl-1,3-dicarbanonaborane,
Tri (butyl) ammoniumundecahydrid-8-ethyl-7,9-dicarbaundecaborate,
4-carbanonaborane (14) bis (tri (butyl) ammonium) nonaborate,
Bis (tri (butyl) ammonium) undecaborate,
Bis (tri (butyl) ammonium) dodecaborate
Bis (tri (butyl) ammonium) decachlorodecaborat,
Tri (butyl) ammonium-1-carbadecaborate,
Tri (butyl) ammonium-1-carbadodecaborate,
Tri (butyl) ammonium-1-trimethylsilyl-1-carbadecaborate,
Tri (buyl) ammonium bis (nonahydrid-1,3-dicarbonnonaborate) cobalt tate (III)
Tri (butyl) ammonium bis (undecahydrid-7,8-dicarbaundecaborate) fer rat (III)
significant.

Combinations of minde are also possible as cocatalyst systems least one of the above amines and a carrier with ele mentorganischen compounds as they be in patent WO 99/40129 are important.

Preferred components of these cocatalyst systems are the compounds of the formulas (A) and (B),

wherein
R ^{17 is} a hydrogen atom, a halogen atom, a group containing C ₁ -C ₄₀ carbon, in particular C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ halo alkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ Aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl or C ₇ -C ₄₀ -haloalkylaryl. R ¹⁷ can also be a -OSiR ₃ group, in which R is the same or different and has the same meaning as R ¹⁷ .

In addition, a further preferred cocatalyst is to be regarded as general compounds which are formed by the reaction of at least one compound of the formula (C) and / or (D) and / or (E) with at least one compound of the formula (F).

R ¹⁷ _v B- (DR ⁷⁰ ) _s (C)

R ¹⁷ ₂ BX ¹ -BR ¹⁷ ₂ (D)

wherein
R ^{70 can be} a hydrogen atom or a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl and in what
R ^{17 has} the same meaning as mentioned above,
X ¹ is an element of the 14th group of the Periodic Table of the Elements or an NR group, wherein R is a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon radical such as C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ aryl .
D is an element of the 14th group of the Periodic Table of the Elements or an NR group, in which R is a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon radical such as C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ aryl,
v is an integer from 0 to 3
s is an integer from 0 to 3,
h is an integer from 1 to 10.

If appropriate, the elemental organic compounds are combined with an organometallic compound of the formulas XI to XIV and or XV [M ⁴⁰ R ¹⁹ _b ] _d , where M ^{40 is} an element from the 1st, 2nd and 11th group of the Periodic Table of the Elements, R ¹⁹ is identical or different and is a hydrogen atom, a halogen atom, a C ₁ -C ₄₀ carbon-containing group, in particular C ₁ -C ₂₀ alkyl, C ₆ -C ₄₀ aryl, C ₇ -C ₄₀ arylalkyl or C ₇ -C ₄₀ alkylaryl group means, b is an integer from 1 to 3 and d is an integer from 1 to 4.

Examples of the cocatalytically active compounds of the formulas A and B are

The organometallic compounds of the formula XV are preferably neutral Lewis acids in which M ^{40 represents} lithium, magnesium and / or aluminum, in particular aluminum. Examples of the preferred organometallic compounds of the formula XII are trimethyl aluminum, triethyl aluminum, tri-isopropyl aluminum, trihexyl aluminum, trioctyl aluminum, tri-n-butyl aluminum, trin-propyl aluminum, triisoprene aluminum, dimethylaluminium monochloride, diethylaluminium monochloride, , Ethylaluminiumsesquichlorid, Dimethylaluminiumhydrid, Diethylaluminium-hydride, Diisopropylalu miniumhydrid, Dimethylaluminium (trimethylsiloxid), Dimethyl-Alu minium (triethylsiloxid), Phenylalan, Pentafluorphenylalan and o-Tolylalan.

As further cocatalysts, the unsupported or supported before may be, are those in EP-A-924223, DE-A-196 22 207, EP-A-601830, EP-A-824112, EP-A-824113, EP-A-811627, WO97 / 11775 and DE-A-196 06 167 compounds to use.

The carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid Be material, especially a porous carrier such as talc, inorganic cal oxides and finely divided polymer powders (e.g. polyolefins).

Suitable inorganic oxides can be found in the 2nd, 11th, 12th, 13th and 14th group of the periodic table and the 3-9 group of the periodic table of the elements. Examples of preferred oxides as carriers include silicon dioxide, aluminum oxide and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for. B. MgO, ZrO ₂ , TiO ₂ or B ₂ O ₃ , to name just a few.

The carrier materials used generally have a specific surface in the range from 10 to 1000 m ² / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size of 1 to 500 μm. Carriers with a specific surface in the range from 50 to 500 μm, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 μm are preferred. Carriers with a specific surface area in the range from 200 to 400 m ² / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 μm are particularly preferred.

If the carrier material used is inherently low Moisture content or residual solvent content can be a Avoid dehydration or drying before use. If not, as when using silica gel as Carrier material, dehydration or drying is recommended mended. Thermal dehydration or drying of the Trä germaterials can under vacuum and at the same time inert gas transfer tion (e.g. nitrogen). The drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical. The drying process can take between 1 and 24 hours be. Shorter or longer drying times are possible provided that under the conditions chosen the equilibrium  weight adjustment with the hydroxyl groups on the carrier surface che can be done, which is usually between 4 and 8 hours calls.

Dehydration or drying of the carrier material is also possible possible chemically by the adsorbed water and the Hydroxyl groups on the surface with suitable inerting be brought to reaction by means. By implementing with the The hydroxyl groups can be completely or inert also partially converted into a form that does not lead to a nega interactions with the catalytically active centers. Suitable inerting agents are, for example, silicon halo genides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, Dimethylaminotrichlorosilane or organometallic compounds of Aluminum, boron and magnesium such as trimethylalu minium, triethyl aluminum, triisobutyl aluminum, triethyl borane, Dibutylmagnesium. Chemical dehydration or inertia tion of the carrier material takes place, for example, in that a suspension of the Trä with exclusion of air and moisture germaterials in a suitable solvent with the inertisie reagent in pure form or dissolved in a suitable solution means to react. Suitable solvents are e.g. B. ali phatic or aromatic hydrocarbons such as pentane, hexane, Heptane, toluene or xylene. Inerting takes place at Tempera doors between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible. The duration of the Reaction is between 30 minutes and 20 hours, preferably 1 up to 5 hours. After the complete expiration of the chemical dehy The carrier material is derivatized by filtration under In conditions isolated, one or more times with suitable iners ten solvents as described above wash and then dry in an inert gas stream or under vacuum net.

Organic carrier materials such as fine-particle polyolefin powder (e.g. polyethylene, polypropylene or polystyrene) can also ver should be used and should also be used before moisture, solvent residues or other contaminants by appropriate cleaning and drying operations become free.

To illustrate the supported catalyst system, min least one of the transition metal compound described above Formula VII in a suitable solvent with at least one Cocatalyst component contacted, preferably a  obtained soluble reaction product, an adduct or a mixture becomes.

The preparation thus obtained is then dehydrated with the or inertized carrier material mixed, the solvent ent distant and the resulting supported transition metal compound Dried catalyst system to ensure that the dissolving medium completely or for the most part from the pores of the Trä germaterials is removed. The supported catalyst is called Get free flowing powder.

A method for producing a free-flowing and optionally prepolymerized transition metal compound catalyst system comprises the following steps:

• a) Preparation of a transition metal compound / cocatalyst Mixture in a suitable solvent or suspension medium, wherein the transition metal compound component is one of the before described structures.
• b) applying the transition metal compound / cocatalyst on a porous, preferably inorganic dehydration based carrier
• c) removing the major portion of solvent from the resultant the mixture
• d) isolation of the supported catalyst system
• e) If necessary, a prepolymerization of the resultant gerten catalyst system with one or more olefini monomer (s) to form a prepolymerized supported Ka to receive the analyzer system.

Preferred solvents for the preparation of the transition metal ver bond / cocatalyst mixture are hydrocarbons and Koh hydrogen mixtures at the selected reaction temperature are liquid and in which the individual components are preferred to solve. However, the solubility of the individual components is not an issue suspension when it is certain that the reaction product is out Transition metal compound and cocatalyst components in the selected solvent is soluble. Examples of suitable solutions agents include alkanes such as pentane, isopentane, hexane, heptane, oc tan and nonan; Cycloalkanes such as cyclopentane and cyclohexane; and  Aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. All toluene is particularly preferred.

The used in the preparation of the supported catalyst system Can set amounts of aluminoxane and transition metal compound can be varied over a wide range. A mo is preferred lar ratio of aluminum to transition metal in the over gear metal connections from 10: 1 to 1000: 1, completely a ratio of 50: 1 to 500: 1 is particularly preferred.

In the case of methylaluminoxane, 30% toluoli are preferred used solutions; the use of 10% solutions is also possible.

For preactivation, the transition metal compound is in the form of egg nes solid in a solution of the aluminoxane in a suitable th solvent. It is also possible to use the transition meter Dissolve the tall compound separately in a suitable solvent and then ver this solution with the aluminoxane solution some. Toluene is preferably used.

The preactivation time is 1 minute to 200 hours.

The preactivation can take place at room temperature (25 ° C). The application of higher temperatures can in individual cases require Shorten the duration of the pre-activation and an additional Increase activity. Higher temperature means in the In this case, a range between 50 and 100 ° C.

The preactivated solution or the transition metal compound / Co catalyst mixture is then with an inert support material, usually silica gel, which is in the form of a dry pul vers or as a suspension in one of the solvents mentioned above is present, united. The carrier material is preferred as a powder used. The order of addition is arbitrary. The preactivated transition metal compound-cocatalyst solution or the transition metal compound-cocatalyst mixture can submitted carrier material dosed, or the carrier material be entered in the submitted solution.

The volume of the pre-activated solution or transition metal compound-cocatalyst mixture can 100% of the total pore volume lumen of the carrier material used or exceed up to 100% of the total pore volume.  

The temperature at which the pre-activated solution or the over gear metal compound cocatalyst mixture with the support material brought into contact can range between 0 and 100 ° C vary. However, lower or higher temperatures are also possible.

Then the solvent becomes complete or the largest Part removed from the supported catalyst system, the Mi Schung stirred and optionally heated. Be both the visible portion of the solvent and is preferred the proportion in the pores of the carrier material is removed. The distance NEN of the solvent can be used in a conventional manner Vacuum and / or purging with inert gas are used. At the Drying process, the mixture can be heated until the free Solvent has been removed, which is usually 1 to 3 hours at a preferably selected temperature between 30 and 60 ° C requires. The free solvent is the visible portion of the solvent medium in the mix. Residual solvent means the type part that is enclosed in the pores.

As an alternative to a complete removal of the solvent the supported catalyst system only to a certain extent Residual solvent content can be dried, the free solvent with tel has been completely removed. Then the drink Catalyst system with a low-boiling hydrocarbon Fabric such as pentane or hexane washed and dried again the.

The supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or before using it in a polymerization process with egg nem or more olefinic monomers are prepolymerized. Execution of prepolymerization of supported catalyst systems is described for example in WO 94/28034.

An additive can be used during or after the preparation of the carrier th catalyst system preferred a small amount of an olefin an α-olefin (for example vinylcyclohexane, styrene or Phe nyldimethylvinylsilane) as a modifying component or an tistatic (as described in US Serial No. 08/365280) added become. The molar ratio of additive to metallocene component Compound I is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.

The present invention also relates to a method for manufacturing position of a polyolefin by polymerization of one or more rer olefins in the presence of the catalyst according to the invention  stems containing at least one transition metal component of Formula VII. The term polymerization is a homopolyme understood as a copolymerization.

Preferably olefins of the formula R _m -CH = CH-R _{n are} polymerized, where rin R _m and R _{n are} identical or different and a hydrogen atom or a carbon-containing radical having 1 to 20 C atoms, in particular 1 to 10 C atoms in particular , mean, and R _m and R _n together with the atoms connecting them can form one or more rings.

Examples of such olefins are 1-olefins with 2-20, preferred have 2 to 10 carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclodode cen or methylnorbornene. Are preferred in the invention processes ethene or propene homopolymerized, or propene with ethene and / or with one or more 1-olefins with 4 to 20 carbon atoms, such as butene, hexene, styrene or vinylcyclohexane, and / or one or more dienes with 4 to 20 carbon atoms, such as 1,4-butadiene, norbornadiene, ethylidene norbone or ethyl norborna serve, copolymerized. Examples of such copolymers are ethene / Propene copolymers, ethene / norbornene, ethene / styrene or ethene / pro pen / 1,4-hexadiene terpolymers.

The polymerization is usually at a temperature of 0 up to 300 ° C, preferably 50 to 200 ° C, very particularly preferably 50 -80 ° C. The pressure is generally 0.5 to 2000 bar, preferably 5 to 64 bar.

The polymerization can be in solution, in bulk, in suspension or in the gas phase, continuously or discontinuously, one or be carried out in several stages.

The catalyst system shown according to the invention can be used as a zige catalyst component for the polymerization of olefins can be used with 2 to 20 carbon atoms, or preferably in combination nation with at least one alkyl compound of the elements from the I. to III. Main group of the periodic table, such as B. an aluminum minium, magnesium or lithium alkyl or an aluminoxane be set. The alkyl compound is the monomer or Sus added a pelletizing agent and serves to purify the monomer of substances that can impair catalyst activity NEN. The amount of alkyl compound added depends on the qua lity of the monomers used.  

As a molecular weight regulator and / or to increase the activity, if necessary, hydrogen is added.

The catalyst system can pure the polymerization system leads or better dosing with inert compo components such as paraffins, oils or waxes. In the Polymerization can also include an antistatic along with or separated from the catalyst system used in the polymer dosing system.

The Po shown with the catalyst system according to the invention polymers show a uniform grain morphology and have none Fine grain fractions. In the polymerization with the fiction According to the catalyst system, there are no deposits or caking on.

The obtained by using the catalyst system according to the invention ten copolymers are with high productivity at technically rele vant process parameters can be produced without deposit formation. You he possible to produce copolymers with high comonomes installation and high molecular weight.

The invention is illustrated by the following, but the invention is not restrictive examples explained.

General information: The production and handling of the organome metallic connections was made in the absence of air and Moisture under argon protective gas (Schlenk technology or glove Box). All required solvents were made with argon before use rinsed and absolute over molecular sieve.

1,2,3,4-tetramethylfulven (1)

2.00 g (0.014 mol) of pentamethylcyclopentadienyllithium (6) and 3.50 g (0.013 mol) of chlorotriphenylmethane are suspended at 0 ° C in a 1: 1 solvent mixture of 50.0 ml of toluene and 50 ml of tetrahydrofuran. The solution is stirred at 5 ° C. overnight, so that a bright red reaction mixture is kept. The suspension is then concentrated to about 20.0 ml and 75.0 ml of pentane are added, the lithium chloride formed in the reaction failing. The precipitate is filtered off and a clear, bright orange solution is obtained. To remove the triphenylmethane formed in the reaction, the reaction solution is concentrated to half the volume and stored at -30 ° C. for 2 days. The triphenylmethane is obtained as a colorless, crystalline solid, which can be separated from the 1,2,3,4-tetramethylfulvene (1) by decanting the supernatant solution. The residues of pentane and tetrahydrofuran are then removed at 0 ° C. in an oil pump vacuum and a toluene solution of the orange-colored product is obtained. Due to the thermolability of the fulvene (1), the product is not completely insulated. To determine the yield or concentration of the compound (1) in solution, the methyl group signal of the toluene against the signals of the methyl groups of the tetramethylfulvene (1) are integrated in the ¹ H-NMR spectrum. The mass fraction of the desired fulvene (1) can be determined from the ratio.
Yield: approx. 1.50 g (approx. 86%).

6,6-dimethylfulven (2)

15.0 ml (12.0 g, 0.21 mol) of acetone and 41.0 ml (0.50 mol) of freshly distilled cyclopentadiene are dissolved in 80.0 ml of degassed methanol and 25.0 ml (0.30 mol) of pyrrolidine are added dropwise with ice cooling. The clearly exothermic reaction is stirred under ice cooling. For working up, neutralize with 18.0 ml of glacial acetic acid (pH control) and add 50.0 ml of water and diethyl ether each. The phases are separated from one another, the aqueous phase is extracted three times with 50.0 ml of diethyl ether, the combined organic phases are first washed with 40.0 ml of water, then with 40.0 ml of saturated sodium chloride solution and dried over magnesium sulfate. The reaction solution is concentrated on a rotary evaporator to a volume of about 50.0 ml and then the remaining ether is removed on the oil pump with ice cooling. The product is obtained as a yellow-orange liquid.
Yield: 15.0 g (70%) (Lit .: 81%).

Lithiumcyclohexylphosphid (3)

60.0 ml (34.8 mmol) of a 0.58 molar cyclohexylphosphine solution in hexane are dissolved in 100 ml of pentane and cooled to -78 ° C. 21.8 ml (34.9 mmol) of n-butyllithium solution are slowly added dropwise to this solution while stirring. The reaction mixture is warmed to room temperature overnight and the isolated colorless lithium salt is then isolated on a frit. The product is washed three times with 20 ml each of pentane and then dried in vacuo.
Yield: 3.71 g (87%).

(Cyclohexylphosphino) methyltetramethylcyclopentadienyllithium (4)

200 mg (2.20 mmol) lithium cyclohexylphosphide (3) are dissolved in 50 ml and cooled to -78 ° C. Then 2.50 g of a 9: 1 mixture of toluene and the 1,2,3,4-tetramethylfulvene (1) are added dropwise. The reaction solution is then warmed to room temperature overnight, the product precipitating out as a white precipitate. The monolithium salt (4) is filtered off, washed twice with 10 ml each of pentane and finally dried in vacuo.
Yield: 410 mg (83%).

¹ H-NMR ([D ₈ ] -tetrahydrofuran, 200.1 MHz, 300 K): δ = 2.10-0.85 (m, 11H, cyclohexyl-H), 1.84, 1.81 (each s, each 6H, Cp-CH ₃ ), 1.72 (d, 2H, ³ J _HH = 6.0 Hz, CH ₂ ).
The PH proton is not observed.
³¹ P NMR ([D ₈ ] tetrahydrofuran, 81.0 MHz, 300 K): δ = -41.2 (dm, 1J _PH = 192 Hz, PH).

(1-methyl-1-cyclohexylphosphinoethyl) cyclopentadienyllithium (5)

200 mg (2.20 mmol) lithium cyclohexylphosphide (3) are dissolved in 50 ml and cooled to -78 ° C. Then 265 mg (2.50 mmol) 6,6-dimethylfulven (2) are added dropwise. The reaction solution is then warmed to room temperature overnight, the product precipitating as a white precipitate. The monolithium salt (5) is filtered off, washed twice with 10 ml each of pentane and finally dried in vacuo.
Note: About 20% of the elimination product (6) is formed as a side reaction.

There is no laborious separation of the by-product at this point, since the connection (6) can be removed more easily in the following stages (second deprotonation, conversion to titanium or zirconium). See below for more information.
Yield (The yield of the lithium salt (5) is determined using ¹ H-NMR spectroscopy. See also note): 357 mg (71%).

¹ H-NMR ([D ₈ ] -tetrahydrofuran, 200.1 MHz, 300 K): δ = 5.62, 5.56 (per m, each 2H Cp-H), 3.00 (d, 1H, ¹ J _PH = 197 Hz, PH) , 1.50, 1.44 (each s, each 3H, CH ₃ ), 1.73-0.81 (m, 11H, cyclohexyl-H).
³¹ P NMR ([D ₆ ] benzene / ([D ₈ ] tetrahydrofuran 4: 1, 81.0 MHz, 300 K): δ = 6.3 (dm, ¹ J _PH = 197 Hz, PH).

Bis (dialkylamido) (η ⁵ : κP-1-phosphidomethylcyclopentadienyl) compounds of titanium and zirconium General procedure for the preparation of the bis (diethyla mido) (η ⁵ : κP-1-phosphidomethylcyclopentadienyl) compounds of titanium and zirconium

A THF solution of the [CpCP] ligand is made at 0 ° C with the equimo laren amount of lithium diisopropylamide, also dissolved in THF, ver sets, stirred for 1 h and then to a solution of bis (dime thylamido) dichlorotitan or bis (diethylamido) dichlorozirconium bis (tetrahydrofuran) in THF. The reaction solution is 2 h stirred, the solvent removed in vacuo and the oily back was recorded in pentane. The failed lithium chloride filtered off and the filtrate dried in vacuo. The zirconium compounds are called bright red-brown oils, the titanium compound isolated as a dark red oil.

Bis (dimethylamido) (η ⁵ : κP-1- (P-cyclohexylphosphido) -1-methylethylidenecyclopentadienyl) titanium

Since the 1- (P-cyclohexyl) phosphino-1-methylethylidency clopentadienyl lithium used. ¹ H-NMR integration still contained 20% 1-methyl vinylcyclopentadienyllithium, correspondingly smaller amounts of lithium diisopropylamide (107 mg, 1 mmol) and bis (dimethylamido) dichlorotitanium (195 mg, 0.95 mmol) were mixed with 250 mg of the mixture of the lithium salts implemented. The 1-methylvinylcyclopentadiene nyllithium did not react and could be separated from the pentane suspension of the product with the lithium chloride.
Yield: 220 mg (0.62 mmol, 65% based on the bis (dimethylamido) dichlorotitanium used).

¹ H NMR ([D ₈ ] toluene, 599.8 MHz, 298 K): δ = 5.69 (m, 2H, 3-H and 4-H), 5.18 (m, 2H, 2-H and 5- H), 2.99 (s, 12H, NCH ₃ ), 1.92 (m, 2H, 2'-H), 1.76 (m, 2H, 3'-H), 1.60 (m, 1H, 4'-H), 1.53 (d, ³ J _PH = 10 Hz, 6H, 7-H), 1.40 (m, 2H, 2'-H), 1.26 (m, 2H, 3'-H), 1.22 (m, 1H, 4'- H), 1.21 (m, 1H, 1'-H).
GCOSY ([D ₈ ] toluene, 599.8 MHz, 298 K): δ ¹ H / δ ¹ H = 5.69 / 5.18 (Cp-H), 1.92 / 1.76, 1.40 (2'-H / 3'-H , 2'-H), 1.76 / 1.92, 1.60, 1.26 (3'-H / 2'-H, 4'-H, 3'-H), 1.60 / 1.76, 1.22 (4'-H / 3'- H, 4'-H), 1.40 / 1.92, 1.26, 1.21 (2'-H / 2'-H, 3'-H, 1'-H).
¹³ C NMR ([D ₈ ] toluene, 150.8 MHz, 298 K): δ = 120.0 (C-1), 110.9 (C-3 and C-4), 107.2 (C-2 and C-5 ), 46.6 (d, ³ J ^PH = 5.2 Hz, NCH ₃ ), 36.7 (d, ¹ J _PC = 38.3 Hz, C-1 '), 34.9 (d, ² J _PC 15.1 Hz, C-2'), 30.5 (C-6), 28.8 (d, ² J _PC = 14.6 Hz, C-7), 27.7 (d, ³ J _PC = 9.3 Hz, C-3 '), 27.0 (C-4').
GHSQC-NMR ([D ₈ ] toluene, 150.8 / 599.8 MHz, 298 K): δ = 110.9 / 5.69 (C-3 and C-4/3-H and 4-H), 107.2 / 5.18 (C -2 and C-5/2-H and 5-H), 46.6 / 2.99 (NCH ₃ ), 36.7 / 1.22 (C-1 '/ 1'-H), 34.9 / 1.92, 1.40 (C-2 '/ 2'-H), 28.8 / 1.53 (C-7/7-H), 27.7 / 1.76, 1.26 (C-3' / 3'-H), 27.0 / 1.60, 1.22 (C-4 '/ 4 '-H).
GHMBC-NMR ([D ₈ ] toluene, 150.8 / 599.8 MHz, 298 K): 8 = 120.0, 30.5 / 1.53 (C-1, C-6/7-H).

¹ H-NMR ([D ₈ ] toluene, 599.8 MHz, 193 K): δ = 5.78, 5.61 (b, each 2H, 3-H and 4-H), 5.33, 4.89 (b, each 2H, 2 -H and 5-H), 3.06, 2.88 (s, each 12H, NCH ₃ ), 2.16 (m, 1H, 1'-H), 2.12 (m, 4H, 2'-H), 1.96 (m, 4H, 3'-H), 1.81 (m, 2H, 4'-H), 1.70 (b, 6H, 7-H), 1.59 (b, 6H, 7-H), 1.46 (m, 4H, 2 ' -H), 1.35 (m, 4H, 3'-H), 1.28 (m, 2H, 4'-H).

¹³ C NMR ([D ₈ ] toluene, 150.8 MHz, 193 K): δ = 120.7 (C-1), 111.2, 110.7 (C-3 and C.4), 108.8, 104.3 (C-2 u . C-5), 47.3, 45.0 (b, NCH ₃ ), 38.5 (C-1 '), 31.9 (C-7), 31.2 (C-2'), 28.3 (C-3 '), 26.4 (C -4 '), 24.4 (C-7), 22.2 (C-6). GHSQC-NMR ([D ₈ ] toluene, 150.8 / 599.8 MHz, 193 K): δ = 111.2 / 5.61 (C-3 or C-4/3-H or 4-H), 110.7 / 5.78 (C -3 or C-4/3-H or 4-H), 108.8 / 4.89 (C-2 or C-5/2-H or 5-H), 104.3 / 5.33 (C-2 or C-5/2-H or 5-H), 47.3 / 2.88 (NCH ₃ ), 45.0 / 3.06 (NCH ₃ ), 38.9 / 2.16 (C-1 '/ 1'-H), 31.9 / 1.70 (C -7 / 7-H), 31.2 / 2.12, 1.46 (C-2 '/ 2'-H), 28.3 / 1.96, 1.35 (C-3' / 3'-H), 26.4 / 1.81, 1.28 (C-4 '/ 4'-H), 24.4 / 1.59 (C-7/7-H).
GHMBC-NMR ([D ₈ ] toluene, 150.8 / 599.8 MHz, 193 K): δ = 120.7 / 1.70, 1.59 (C-1, 7-H), 22.2 / 1.70 (C-6, 7-H).
³¹ P NMR ([D ₈ ] toluene, 81.0 MHz): δ = 14.2 (298 K), 6.3 (273 K), 0.6 (253 K), -5.5 (233 K), -11.4 (213 K), -17.2 (193 K).

Result of dynamic ¹ H-NMR spectroscopy ([D ₈ ] toluene, 599.8 MHz): Δν of the Cp resonances (T = 193 K) = 93 Hz (5.78 / 5.61) or 272 Hz (5.33 / 4.89).
Coalescence temperature T _c = 213 K or 228 K.
ΔG ^≠ = 9.8 kcal mol ^-1 or 10.0 kcal mol ^-1
Elemental analysis:
calculated:
C: 60.67%; H: 9.33%; N: 7.86%;
found:
C: 61.98%; H: 9.15%; N: 5.53%.

Bis (diethylamido) (η ⁵ : κP-1- (P-cyclohexylphosphido) -1-methylethylidenecyclopentadienyl) zirconium

Analogously to the synthesis of the titanium compound, 250 mg of the mixture with 107 mg of lithium diisopropylamide (1 mmol) and 430 mg of bis (diethy lamido) dichlorozirconium bis (tetrahydrofuran) (0.95 mmol) are reacted, taking into account the contamination of the lithium salt. The product is obtained as a red oil.
Yield: 312 mg (0.67 mmol, 72% based on bis (diethylamido) dichlorozirconium bis (tetrahydrofuran))

¹ H-NMR ([D ₈ ] toluene, 03558 00070 552 001000280000000200012000285910344700040 0002010054649 00004 03439599.8 MHz, 298 K): δ = 5.92 (m, 2H, 3-H and 4-H), 5.47 (m, 2H, 2 -H and 5-H), 3.26, 3.15 (m, each 4H, NCH ₂ ), 1.99 (m, 2H, 2'-H), 1.76 (m, 2H, 3'-H), 1.62 (d, ³ J _PH = 10 Hz, 6H, 7-H), 1.60 (m, 1H, 1'-H), 1.58 (m, 1H, 4'-H), 1.47 (m, 2H, 2'-H), 1.26 (m, 2H, 3'-H), 1.23 (m, 1H, 4'-H), 0.93 (t, 3J = 6.0 Hz, 6H, NCH ₂ CH ₃ ).
GCOSY ([D ₈ ] toluene, 599.8 MHz, 298 K): δ ¹ H / δ ¹ K = 5.92 / 5.47 (Cp-H),
¹³ C NMR ([D ₈ ] toluene, 150.8 MHz, 298 K): 124.0 (C-1), 108.1 (C-3 and C-4), 106.4 (d, ³ J _PC = 3.6 Hz, C -2 and C-5), 42.5 (d, ³ J _PC <2 Hz, NCH ₂ ), 36.0 (d, ² J _PC = 16 Hz, C-2 '), 35.6 (d, ¹ J _PC = 38 Hz, C-1 '), 33.2 (C-6), 30.9 (d, ² J _PC = 13 Hz, C-7), 27.6 (d, ³ J ^PC = 11 Hz, C-3'), 26.9 ( C-4 '), 16.1 (NCH ₂ CH ₃ ).
GHSQC-NMR ([D ₈ ] toluene, 150.8 / 599.8 MHz, 298 K): δ = 108.1 / 5.92 (C-3 and C-4/3-H and 4-H), 106.4 / 5.47 (C -2 and C-5/2-H and 5-H), 42.5 / 3.26, 3.15 (NCH ₂ ), 36.0 / 1.99, 1.47 (C-2 '/ 2'-H), 35.6 / 1.60 (C -1 '/ 1'-H), 30.9 / 1.62 (C-7/7-H), 27.6 / 1.76, 1.26 (C-3' / 3'-H), 26.9 / 1.58, 1.23 (C-4 ' / 4'-H), 0.93 (NCH ₂ CH ₃ / NCH ₂ CH ₃ ).
GHMBC-NMR ([D ₈ ] toluene, 150.8 / 599.8 MHz, 298 K): δ = 124.0, 33.5 / 1.62 (C-1, C-6/7-H).
³¹ P NMR ([D ₈ ] toluene, 81.0 MHz): δ = -11.5 (298 K), -14.5 (273 K), -16.9 (253 K), -19.1 (233 K), -21.5 (213 K), -24.2 (193 K).
Elemental analysis:
calculated:
C: 57.98%; H: 9.07%; N: 6.15%;
found:
C: 58.27%; H: 8.61%; N: 4.91%.

Bis (diethylamido) (η ⁵ : κP-1- (P-cyclohexylphosphido) methyli-2,3,4,5-tetramethylcyclopentadienyl) zirconium

257 mg (1 mmol) 1- (P-cyclohexyl) phosphinomethyl-2,3,4,5-tetrame thylcyclopentadienyllithium are mixed with 107 mg lithium diisopropyl amide (1 mmol) and 430 mg bis (diethylamido) dichlorozirconium bis (tetrahydrofuran) ( 0.95 mmol) to a red-brown oil.
Yield: 245 mg (71 mmol, 75% based on bis (the thylamido) dichlorozirconium bis (tetrahydrofuran)) used.

¹ H-NMR ([D ₆ ] -benzene, 200.13 MHz): δ = 3.47-3.22 (m, 8H, NCH ₂ ), 2.22-1.02 (m, 11H, C ₆ H ₁₁ ), 1.99 (s, 6H, CH ₃ ), 1.97 (s, 6H, CH ₃ ), 1.06 (t, 3J = 6.6 Hz, 12H, NCH ₂ CH ₃ ).
³¹ P NMR ([D ₆ ] benzene, 81.0 MHz): δ = -106.4.

Homopolymerization of norbornene

20 mg of catalyst are added to a solution of 1.75 g of norbornene in 30 ml of a 10% strength MAO solution at 80 ° C. and the mixture is stirred for 20 hours. The mixture is then hydrolysed with 20 ml of MeOH / 1N HCl 1: 1, stirred with half-concentrated HCl and the polymer is filtered, washed and dried.

Polymerization of ethene

Copolymerizations ethylene / 1-octene

Claims (6)

1. Process for the preparation of compounds of formula (VII)
wherein
R ^{30 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ - to C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing Is C ₇ -C ₂₀ alkyl aryl, where the R ³⁰ ligands are identical or different,
R ² , R ³ , R ⁴ , R ^5, identical or different, represent a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ - to C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, is fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ alkylaryl, the radicals R ² , R ³ , R ⁴ and R ⁵ can form cyclic systems with one another, which in turn are substituted,
R ^{6 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ - to C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl,
R ^{10 is} a hydrogen atom, a halogen atom, C ₁ -C ₁₈ alkyl, C ₃ - to C ₁₂ -cycloalkyl, a C ₆ -C ₂₀ aryl, a C ₆ -C ₂₀ aryloxy group, a C ₁ -C ₂₀ alkyloxy group, a nitrogen-containing compound,
Z is phosphorus, oxygen, nitrogen and sulfur,
M ^{4 is} an element of the 3rd to 8th group of elements of the periodic system,
comprehensively the steps

• A) implementation of a compound of formula I.
  wherein,
  R ¹ identical or different, a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ - to C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkyl alkenyl, C ₆ -C ₁₈ - Aryl, C ₅ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ alkylaryl and R ² , R ³ , R ⁴ , R ^{5 have} the meaning given under formula (VII),
  X is oxygen, nitrogen and sulfur,
  y is 1 or 2,
  R ^{30 has} the meaning given above,
  with a compound of formula (II),
  M ¹ R ⁶ ZR ⁷ (II)
  wherein
  Z and R ^{6 have} the meaning given under formula (VII),
  M ^{1 is} an element of the 1st or 2nd group of the Periodic Table of the Elements,
  R ^{7 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing Is C ₇ -C ₂₀ alkyl aryl, to a compound of formula (III)
  wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ³⁰ , Z, M ¹ and y have the meanings described above
• B) reaction of the compound of formula (III) obtained in step A) with an organometallic compound of formula IV
  M ² R ⁸ (IV)
  wherein
  M ^{2 is} an element of the 1st or 2nd group of the Periodic Table of the Elements,
  R ^{8 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, to give a compound of the formula (V)
  wherein
  R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ³⁰ , Z and y have the meaning described above and
  M ^{3 is} an element of group 1 or 2 of the Periodic Table of the Elements,
• C) reaction of the compound of formula (V) obtained in step B) with a compound of formula (VI)
  M ⁴ (R ⁹ ) _f (R ¹⁰ ) _g (R ¹¹ ) _k (VI)
  wherein
  M ^{4 is} an element of the 3rd to 8th group of elements of the periodic system,
  R ^{9 is} a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ carbon group, a C ₅ -C ₂₀ aryl, a C ₅ -C ₂₀ aryloxy group, a C ₁ -C ₂₀ alkyloxy,
  R ^{10 is} a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ carbon group, a C ₅ -C ₂₀ aryl, a C ₅ -C ₂₀ aryloxy group, a C ₁ -C ₂₀ alkyloxy,
  R ^{11 is} C ₁ -C ₂₀ heterocarbon compound,
  f is a number from 1-10,
  g is a number from 1-10,
  k is a number from 1-10,
  to the compound of general formula (VII) according to the invention.

2. The method according to claim 1, characterized in that instead of a compound of formula I, a compound of formula VIII
wherein,
R ²⁰ C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ - Is alkylaryl and R ² , R ³ , R ⁴ , R ^{5 have} the meaning given under formula (VII),
with a compound of formula (II),
M ¹ R ⁶ ZR ⁷ (II)
wherein
Z, R ⁶ , M ¹ and R ^{7 have} the meanings given above, to give a compound of the formula (IX)
wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ²⁰ , R ³⁰ , Z, M ^{1 have} the meanings described above and
R ^{21 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ Heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C. ₇ -C ₂₀ alkyl is aryl,
implemented and subsequently with an organometallic compound of formula X
M ⁵ R ²² (X)
wherein
M ^{2 is} an element of the 1st or 2nd group of the Periodic Table of the Elements,
R ^{22 is} a C ₁ -C ₂₀ carbon-containing group, or an N (R ⁵⁰ ) _p unit in which R ^{50 is} preferably C ₁ -C ₁₈ alkyl, and p 2 is,
to the compound of formula V described above. 3. Compound of Formula (VII-A)
wherein
R ^{30 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ Heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C. ₇ -C ₂₀ alkyl aryl, wherein the R ³⁰ substituents not common to have the same meaning when Z = nitrogen, said R ³⁰ substituents together the same significance can have tung when Z = phosphorus,
R ² , R ³ , R ⁴ , R ^{5 are} identical or different, a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl , C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₁ -C ₁₂ alkyl, fluorine-containing C ₆ -C ₁₈ Aryl, fluorine-containing C ₇ -C ₂₀ arylalkyl or fluorine-containing C ₇ -C ₂₀ alkylaryl is the radicals R ² , R ³ , R ⁴ and R ⁵ can form cyclic systems with one another, which in turn can in turn be substituted,
R ^{6 is} a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₁₈ aryl, C ₅ -C ₁₈ - heteroaryl, C ₇ -C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl,
R _{10 is} a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ carbon group, a C ₆ -C ₂₀ aryl, a C ₆ -C ₂₀ aryloxy group, a C ₁ -C ₂₀ alkyloxy group,
Z is phosphorus, oxygen, nitrogen and sulfur,
M ^{4 is} an element of the 3rd to 8th group of elements of the periodic system. 4. Containing catalyst system

• A) at least one cocatalyst,
• B) at least one compound of the formula (VII) according to claim 1,
• C) optionally at least one carrier.

5. Use of the compound (VII) according to claim 1 for the polymer rization of olefins. 6. Use of the catalyst system according to claim 4 for poly merization of olefins.