EP1401848A1 - Non-metallocenes, method for the production thereof and use thereof in the polymerization of olefins - Google Patents

Abstract

The invention relates to a novel group of special transition metal compounds and catalyst systems produced therefrom. Said novel catalyst systems are suitable for the polymerization of olefins.

Description

 description

Non-metallocenes, processes for their preparation and their use in the polymerization of olefins

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

In recent years, olefin polymerization has been used alongside conventional Ziegler

Catalysts Metallocenes are used to generate polyolefins with special properties that cannot be achieved with conventional Ziegler catalysts. Metallocenes, optionally in combination with one or more cocatalysts, can be used as a catalyst component for the polymerization and copolymerization of olefins. In particular, as

Halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex.

The representation and use of metallocenes still represents one today

Represents a cost factor that could not be overcome by increased activity or improved synthetic methods. In addition, the heterogenization of such catalysts is a further problem, since the activities in particular suffer a sharp drop compared to the homogeneously conducted polymerization.

Various “non-metallocenes” are described in the literature, for example in EP 874 005, which are notable for advantages in the representability and the cost of the educts. The high activities of these complexes represent a further cost-saving factor. Despite numerous compounds known from the literature, such as e.g. in J. Organomet. Chem. 1999, 587, 58-66 and Organometallics 2001, 20, 408-

417, however, it has so far not been possible to develop “non-metallocenes” that generate isotactic polypropylene with sufficient tacticity. It was therefore the task of developing new metal catalysts which enable new advantageous access to polyolefins and at the same time avoid the disadvantages of the prior art described.

Surprisingly, it has now been found that sales of bridged

Ligands with transition metal compounds provide chiral transition metal complexes that are capable of stereospecifically polymerizing propene. This type of representation represents universal access to these new types of connection. The object underlying the invention is thus achieved by these connections.

The present invention relates to compounds of the formula I.

Formula I wherein

M ^{1 is} a metal of III. to XII. Group of the Periodic Table of the Elements, in particular Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd or Cu and D ^{1 is the} same or different and a donor atom of the XV and XVI. Group of the Periodic Table of the Elements, in particular N, P, As, O, S, Se and Te and D ^{2 is the} same or different and a donor atom of XV and XVI. Group of the Periodic Table of the Elements, in particular N, P, As, O, S, Se and Te and Z is a bridging structural element between the two donor atoms D ¹ and X is the same or different and a hydrogen atom, a C Cιo-

Hydrocarbon group such as Cι-Cιo-alkyl, C ₆ -Cιo-aryl, C ₇ -C ₂ o-alkylaryl, C ₇ - C ₂₀ arylalkyl, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂ o-alkynyl or a halogen atom, or OR ⁶ , SR ⁶ , OS0 ₂ R ⁶ , OSi (R ⁶ ) ₃ , Si (R ⁶ ) ₃ , P (R ⁶ ) ₂ , P (R ⁶ ) ₃ , NCR ⁶ , N (R ⁶ ) ₃ , B (R ⁶ ) ₄ , substituted or unsubstituted pyridine or N (R ⁶ ) ₂ , and R ^{1 is the} same or different and are a hydrogen atom, a Cι-C ₂ o alkyl group, a C ₆ -C ₂ n-aryl group, a C -C ₂ o-alkylaryl group, a C ₇ -C ₃ o-

Arylaikylgruppe, a C ₂ -C ₂ o-Alkeny! Group, a C ₂ -C ₂₀ -Alkiny! Group or a halogen-containing -C-C ₂₀ alkyl group, C6-C ₂₀ aryl group, C ₇ -C ₂₀ - alkylaryl group, C ₇ to C ₃₀ arylalkyl group, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂₀ - alkynyl group or a heteroatom-containing C-ι-C ₂ o alkyl group, C ₆ -C ₂₀ - aryl group, C ₇ -C ₂ o -Alkylaryl group, C -C _3u -arylalkyl group, C ₂ -C ₂₀ -

Alkenyl group, C ₂ -C ₂ o-alkynyl group or Si (R ⁶ ) ₃ , where one or more radicals R ¹ with one or more radicals R ^{2 can form} a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or isoquinolinyl , which in turn can be substituted by one or more radicals R ⁶ , and

R ^{2 is the} same or different and a hydrogen atom, a -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C -C ₂₀ alkylaryl group, a C -C ₃ o-arylalkyl group, a C ₂ -C ₂ o-alkenyl group, a C ₂ -C ₂ r _{j: j} alkynyl group or a halogen-containing C ₁ -C ₂₀ alkyl group, C ₆ -C ₂ o aryl group, C ₇ -C ₂ o alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ -

Alkynyl group or a heteroatom-containing CC ₂ o -alkyl group, C ₆ -C ₂₀ aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group or Si (R ⁶ ) ₃ means, where one or more radicals R ² with one or more radicals R ¹ and / or R ^{3 is} a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or

Isoquinolinyl, may form which may itself be substituted by one or more radicals R ^6, and R ^{3 are} identical or different and are a hydrogen atom, a Cι-C ₂ o alkyl group, a C ₆ -C ₂ o-aryl group, a C ₇ -C ₂₀ alkylaryl group, a C ₇ -C ₃₀ - aralkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group or a halogen-containing C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ - Aryl group, C ₇ -C ₂ o -alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂ o-alkenyl group, C ₂ -C ₂₀ alkynyl group or a heteroatom-containing C ₁ -C ₂₀ alkyl group, C ₆ - C ₂₀ - ar l group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ - Alkenyl group, C ₂ -C ₂₀ alkynyl group or Si (R ⁶ ) ₃ , where one or more radicals R ³ with one or more radicals R ^{2 can form} a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or isoquinolinyl, which in turn can be substituted by one or more R ⁶ radicals, and

R ^{4 is the} same or different and is a hydrogen atom, a C ₁ -C ₂₀ -alkyl group, a C ₆ -C ₂ o-aryl group, a C ₇ -C ₂₀ alkylaryl group, a C ₇ -C ₃₀ arylalkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂ o-alkynyl group or a halogen-containing -C-C ₂₀ alkyl group, C ₆ -C ₂₀ aryl group, C -C ₂ o- alkylaryl group, C -C ₃ o-arylalkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ -

Alkynyl group or a heteroatom-containing C-ι-C ₂ o alkyl group Ce-C ₂ o aryl, C ₇ -C ₂₀ -alkylaryl, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ - alkenyl or C ₂ -C ₂₀ alkynyl group, and R ⁵ are identical or different and are a hydrogen atom, a Cι-C ₂ o alkyl group, a C ₆ -C ₂ o-aryl group, a C ₇ -C ₂₀ alkylaryl group, a C ₇ -C ₃₀ -

Arylalkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group or a halogen-containing Cι-C ₂₀ alkyl, C ₆ -C ₂₀ aryl group, C7-C ₂₀ - alkylaryl, C ₇ -C ₃₀ - Arylalkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group or a heteroatom-containing C ₁ -C ₂ rj alkyl group, C6-C20 aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C2-C ₂ 0-

Alkenyl group, C ₂ -C ₂₀ alkynyl group, where several R ⁵ radicals can form a mono- or polycyclic ring system with one another, and R ^{6 are the} same or different and a hydrogen atom, a halogen atom, a C1-C1 ₀ alkyl group, a C ₆ -C ₂ o-aryl group, a C ₇ -C ₂₀ alkylaryl group, a C ₇ -C ₃₀ arylalkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂ o-alkynyl group or a halogen-containing C ₁ -C ₂ o-alkyl group, C ₆ -C ₂ o-aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂ o-alkynyl group or a hetero atom-containing Cι. _C20 alkyl group, C6-C ₂₀ - aryl group, C ₇ -C ₂₀ alkylaryl group, C ₃ -C o-arylalkyl group, C ₂ -C ₂₀ - alkenyl, C ₂ -C ₂₀ alkynyl group, and a respectively equal to or are different and are an integer from 1 to 10 and b are each the same or different and are an integer from 0 to 3 and c are each the same or different and represent an integer from 0 to 2 and d are each identical or different and represent an integer from 0 to 2 and e are each identical or different and represent an integer from 0 to 2 and f each are the same or different and represent an integer from 2 to 20 and g are each the same or different and represent 1 or 2 and h are each identical or different and represent an integer from 1 to 4 and i are each identical or different and one are an integer from 0 to 24 and j are each the same or different and are an integer from 0 to 10,

with the proviso that complexes in which Z _a (R ⁵ ) _{f is} unsubstituted or substituted ethyl, and D ¹ is nitrogen, R ³ is hydrogen, d is 1 and two R ² together form a substituted benzene ring , which is substituted by D ² is oxygen, so-called salen complexes, are excluded from the invention.

Illustrative but non-limiting examples of D ¹ -Z ¹ (R ⁵ ) fD ¹ are:

II a II b II c II d II e II f II h II i

ll p II q II r II t

II u II v II w ll x H y ii z

Formula II a - z

Transition metal compounds of the formula I in which are preferred

M ^{1 is} a metal of III. to XII. Group of the Periodic Table of the Elements is, in particular Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe., Ru, Co, Rh, Ni, Pd or Cu and D ^{1 is the} same or different and a donor atom of XV. and XVI. Group of

Periodic table of the elements, in particular N, P, O and S, and D ^{2 is} identical or different and a donor atom of XV. and XVI. Group of the Periodic Table of the Elements, in particular N, P, O and S, and Z is a bridging structural element between the two donor atoms D ¹ , in particular formula !! a - z, and X is the same or different and is a Cι-Cι ₀ -hydrocarbon group such as C-Cs alkyl, C ₆ -C ₁₀ aryl, CrCu-alkylaryl, _C7-Cn aralkyl, C ₂ -Cι ₀ - Alkenyl, C ₂ -Cι ₀ - alkynyl or a halogen atom, or OR ⁶ , SR ⁶ , OS0 ₂ R ⁶ , OSi (R ⁶ ) ₃ , Si (R ^δ ) ₃ , P (R ⁶ ) ₂ , P (R ⁶ ) 3, NCR ⁶ , N (R ⁶ ) ₃ , B (R ⁶ ) ₄ , substituted or unsubstituted.es

Is pyridine or N (R ⁶ ) ₂ , and R ^{1 is} identical or different and is a hydrogen atom, a C ₁₀ -C ₁₀ alkyl group, a C ₆ -C ₁₀ aryl group, a C ₇ -C 8 alkylaryl group, a C -Cn- Ar lalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cιo alkynyl group or a halogen-containing Cι -Cι ₀ alkyl group, C ₆ -C ₁₀ aryl group, C ₇ -Cn-

Alkylaryl group, C ₇ -Cn-arylalkyl group, C ₂ -Cι ₀ alkenyl group, C ₂ -C ι ₀ - alkynyl group or a heteroatom-containing Cι-C ₁₀ alkyl group, C ₆ -C ₁₀ aryl group, C ₇ -Cn alkylaryl group , C ₇ -Cn arylalkyl group, C ₂ -C ₀ alkenyl group, C ₂ -Cιo alkynyl group or Si (R ⁶ ) ₃ , where one or more radicals R ¹ with one or more radicals R ^{2 is} a mono- or polycyclic Ring system, such as pyridinyl, quinolinyl or isoquinolinyl, can form, which in turn can be substituted by one or more radicals R ⁶ , and R ^{2 is the} same or different and a hydrogen atom, a -C ₁₀ alkyl group, a Cβ-Cio- Aryl group, a C -Cn alkylaryl group, a C ₇ -Cn

Arylalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -C ₁₀ alkynyl group or a halogen-containing CrCio alkyl group, C ₆ -Cι ₀ aryl group, C ₇ -Cιr alkylaryl group, C ₇ -Cn arylalkyl group, C ₂ - C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group or a hetero atom-containing CrC ₁₀ alkyl group, C ₆ -C ₁₀ aryl group, C ₇ -Cn alkylaryl group, C ₇ -Cn arylalkyl group, C ₂ -Cιo-

Alkenyl group, C ₂ -Cιo-alkynyl group or Si (R ⁶ ) ₃ , where one or more radicals R ² with one or more radicals R ¹ and / or R ^{3 is} a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or Isoquinolinyl, which in turn can be substituted by one or more radicals R ⁶ , and R ^{3 is the} same or different and a hydrogen atom, a CrC ₁₀ alkyl group, a C ₆ -Cι ₀ aryl group, a C ₇ -Cn- alkylaryl group, a C ₇ -C ₁₁ - aralkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cι ₀ alkynyl group or a halogen-containing Cι-Cι ₀ alkyl, C ₆ -Cιo-ary group, C7-C! ₁₁ - alkylaryl group, C ₇ -Cπ arylalkyl group, C ₂ -Cι ₀ alkenyl group, C ₂ -Cι ₀ - alkynyl group or a heteroatom-containing Ci-C-to-alkyl group, C ₆ -Cιo- aryl group, C ₇ -C -ιι -Alkylarylgruppe, C ₇ -Cn-arylalkyl group, C ₂ -C ₁₀ - alkenyl group, C ^ CurAlkinylgruppe or Si (R ⁶ ) ₃ , wherein one or more radicals R ³ with one or more radicals R ^{2 is} a mono- or polycyclic ring system , such as pyridinyl, quinolinyl or isoquinolinyl, which in turn can be substituted by one or more radicals R ⁶ , and R ^{4 are the} same or different i st and a hydrogen atom, a CrCio-alkyl group, a Ce-Cio-aryl group, a C ₇ -Cn alkylaryl group, a C ₇ -Cn arylalkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cιo alkynyl group or a halogen-containing CrCio-alkyl group, C ₆ -Cιo-aryl group, C -Cn-alkylaryl group, C ₇ -Cn-arylalkyl group, C ₂ -Cι ₀ -alkenyl group, C ₂ -C-ιo-alkynyl group or a heteroatom-containing CrCio-alkyl group, C ₆ -Cιo-

Aryl group, C ₇ -Cιι-alkylaryl, _C7-Cn arylalkyl group, C ₂ -C ₁₀ - alkenyl or C ₂ -Cι ₀ alkynyl group, and R ⁵ are identical or different and are a hydrogen atom, a G ₁ -C 1 ₁ -

Alkyl group, a C ₆ -Cιo-aryl group, a C Cn-alkylaryl group, a C ₇ -C ₁₁ - aralkyl group, a C ₂ -Cι ₀ alkenyl group, a C ₂ -Cι ₀ alkynyl group or a halogen-containing CrCio-alkyl group, C ₆ -Cι ₀ aryl group, C ₇ -C ₁₁ - alkylaryl, C ₇ d - «- arylalkyl group, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ - alkynyl group or a heteroatom-containing CrCio-alkyl, C ₆ - C ₁₀ - aiyl group, C ₇ -C ₁ alkylaryl group, C ₇ -C ₁₁ arylalkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -Cι ₀ alkynyl group, with several R ⁵ radicals forming a mono- or polycyclic ring system with one another and R ^{6 are the} same or different and represent a hydrogen atom, a halogen atom, a C ₁ -C10 alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₂₀ alkylaryl group, a C ₇ -C ₃₀ arylalkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group or a halogen-containing CC ^ alkyl group, C ₆ -C ₂₀ aryl group, C ₇ -C ₂₀ -

Alkylaryl group, C -C ₃₀ arylalkyl group, C ₂ -C ₂ o-alkenyl group, C ₂ -C ₂₀ -

Alkynyl group or a hetero atom-containing C ₂₀ alkyl group, C ₆ -C ₂₀ -

Aryl group, C ₇ -C ₂ o-alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂ o-alkenyl group, C ₂ -C ₂₀ alkynyl group, and a are each the same or different and an integer of 1 to 4 and b are each the same or different and are an integer from 0 to 2 and c are each the same or different and are an integer from 0 to 2 and d are each the same or different and an integer from 0 to 2 and e are the same or different and are an integer from 0 to 2 and f are each the same or different and are an integer from 2 to 20 and g are each the same or different and 1 or 2 and h are each the same or are different and are an integer from 1 to 4 and i are each the same or different and are an integer from 0 to 24 and j are each the same or different and are an integer from 0 to 10,

with the proviso that complexes in which Z _a (R ⁵ ) _{f is} unsubstituted or substituted ethyl, and D ¹ is nitrogen, R ³ is hydrogen, d is 1 and two R ² together form a substituted benzene ring which is substituted by D ² is oxygen, so-called salen complexes, are excluded from the invention.

Compounds of the formula I in which M ^{1 is} a metal of III. to XII. Group of the Periodic Table of the Elements, in particular Ti, Zr, Hf, Fe, Co, Ni or Pd and D ^{1 is the} same or different and a donor atom of XV. and XVI. Group of

Periodic table of the elements, in particular N, P, O and S, and D ^{2 is} identical or different and a donor atom of XV. and XVI. Group of

Periodic table of the elements is, in particular N, P, O and S, and Z corresponds to the formulas II d, II j, II o, II r or II s and X is the same or different and chloride, bromide, iodide, methyl, ethyl Propyl

Ethenyl, propynyl, phenyl, benzyl, methoxy, trifluoromethanesulfonyl, dimethylamido, tetrafluoroborate, triphenylphophine, acetonitrile, trimethylsilyl or pyridine, and R ^{1 is the} same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, or a radical R ¹ with a radical R ^{2 forms} a mono- or polycyclic ring system, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn is represented by one or more radicals R. ⁶ can be substituted, and R ^{2 is the} same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, or a radical R ² with a radical R ^{1 forms} a mono- or polycyclic ring system, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn is represented by one or more radicals R. ⁶ can be substituted, and R ^{3 is the} same or different and represents a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, and R ^{4 is the} same or different and is a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, and R ^{5 is the} same or different and is a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, or where several radicals R ⁵ can form a mono- or polycyclic ring system with one another, and R ^{s is} identical or different and is a hydrogen atom, fluorine, chlorine, bromine, iodine,

Is methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, and a is the same or different and 1 or 2 and b is the same or different and is an integer from 0 to 2 and c is the same or different and is an integer from 0 to 2 and d is the same or different and are an integer from 0 to 2 and e are each the same or different and are 0 or 1 and f are each the same or different and are an integer from 2 to 20 and g are each the same or different and 1 or 2 is and h are in each case identical or different and denote an integer from 1 to 4 and i are each identical or different and denote an integer from 0 to 18 and j are each identical or different and denote an integer from 0 to 6,

with the proviso that complexes in which Z _a (R ⁵ ) _{f is} unsubstituted or substituted or ethyl, and D ¹ is nitrogen, R ³ is hydrogen, d is

1 is and two R ² together form a substituted benzene ring which is substituted by D ² is oxygen, so-called salen complexes, are excluded from the invention.

Illustrative but non-limiting examples of compounds of formula 1 are:

as well as the corresponding iron, cobalt, nickel and palladium complexes and the corresponding complexes in which X has the meaning given above.

Further illustrative, but not limiting examples of compounds of the formula! are:

in which Bn stands for benzyl, and the corresponding titanium and hafnium complexes and the corresponding complexes in which X has the meaning given above.

Synthesis Examples:

FeCI ₂ Zr (Bn),

THF toluene

84% 74%

The ligands with bisimine structure can be obtained by condensing bisamines with aldehydes or ketones. The bisamine ligands are obtained by reducing the corresponding bisimines or by alkylating bisamines with common alkylation reagents, e.g. Arylalkyl halides, prepared with the addition of bases in a solvent. The reaction of bisimines with transition metal salts, e.g. with iron (II) chloride, nickel (II) bromide * DME, cobalt (II) chloride or bisacetonitrile palladium dichloride in a solvent, e.g. Tetrahydrofuran or dichloromethane, provides the corresponding

Transition metal complexes. The reaction of ligands with a bisamine structure with transition metal compounds, such as, for example, tetrabenzylzircon, tetrakis (dimethylamido) zircon, tetrabenzyltitanium, tetrakis (dimethylamido) titanium, Tetrabenzylhafnium or tetrakis (dimethylamido) hafnium, in a solvent such as benzene, toluene or tetrahydrofuran provides the corresponding transition metal complexes. Furthermore, complexes of this type can be obtained by deprotonation of the bisamine ligand with a base in a solvent, such as toluene or THF, or solvent mixtures, followed by the conversion with

Transition metal halide dides such as e.g. Zirconium tetrachloride, titanium tetrachloride, or hafnium tetrachloride can be obtained.

Salenes, ie complexes in which Z _a (R ⁵ ) _f denotes unsubstituted or substituted ethyl, and D ¹ are nitrogen, R ³ are hydrogen and d are the same

1 is and two R ² together form a substituted benzene ring which is substituted by D ² as oxygen, and the following complexes are excluded:

[(S0 ₃ CF ₃ ) ₂ ]

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

The metal complexes of the formula I according to the invention are particularly suitable as a constituent of catalyst systems for the preparation of polyolefins by polymerizing at least one olefin in the presence of a catalyst which contains at least one cocatalyst and at least one metal complex of the formula I.

The cocatalyst which, together with a transition metal complex of the formula I according to the invention, forms the catalyst system, contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound which, by reaction with a metal complex, converts the latter into a cationic compound.

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

(R AIO) _n (III) used.

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

or linear as in formula (V)

or of the cluster type as in formula (VI)

(VI). Such aluminoxanes are described, for example, in JACS 117 (1995), 6465-74,

Organometallics 13 (1994), 2957-2969.

The radicals R in the formulas (III), (IV), (V) and (VI) can be the same or different and a Ci ^ rj hydrocarbon group such as a C- | -C ₆ alkyl group, a C _Q - C- 18-aryl group, benzyl or hydrogen, and p is an integer from 2 to

50, preferably 10 to 35 mean.

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 hydrogen or isobutyl or n-

Butyl preferably 0.01 to 40% (number of radicals R) are contained.

The aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminium hydrocarbon compound with water (gaseous, solid, liquid or bound - for example as water of crystallization) 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 (see p.

Pasyπkiewicz, Polyhedron 9 (1990) 429 and EP-A-0,302,424).

Regardless of the type of production, all aluminoxane solutions have in common a changing content of unreacted aluminum starting compound, which is present in free form or as an adduct.

As Lewis acid preferably at least one organoboron or organoaluminum compound is used, the C _j ^ n-carbonaceous groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl or 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 (tolis), borane 5-dimethylphenyl) borane, tris (3,5-difluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Is particularly preferred

Tris (pentafluorophenyl) borane.

Compounds which contain a non-coordinating anion, such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF ₆ ^~ , CF3SO3- or CIO4-, are preferably used as ionic cocatalysts.

Protonated Lewis bases such as methylamine, aniline, N, N-dimethylbenzylamine and derivatives, N, N-dimethylcyclohexylamine and derivatives, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N- are used as cationic counterions. Dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene or triphenylcarbene used.

Examples of such ionic compounds are

Triethylammonium tetra (phenyl) borate,

Tributylammoniumtetra (phenyl) borate,

Trimethylammonium tetra (tolyl) borate, tributylammonium tetra (tolyl) borate,

Tributylammonium tetra (pentafluorophenyl) borate,

Tributylammonium tetra (pentafluorophenyl) aluminate,

Tripropylammoniumtetra (dimethylphenyl) borate,

Tributylammonium tetra (trifluoromethylphenyl) borate, tributylammonium tetra (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, N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borates,

N, N-Dimethylbenzylammoniumtetrakis (pentafluorophenyl) borate,

Di (propyl) ammoniumtetrakis (pentafluorophenyl) borate,

Di (cyclohexyl) ammoniumtetrakis (pentafluorophenyl) borate,

Triphenylphosphonium tetrakis (phenyl) borate, triethylphosphonium tetrakis (phenyl) 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 and / or are preferred N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

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

Borane or carborane compounds such as e.g.

7,8-dicarbaundecaborane (13),

Undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,

Dodecahydrid-1-phenyl-1, 3-dicarbanonaborane, tri (butyl) ammonium undecahydrid-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) decachlorodecaborate, tri (butyl) ammonium-1-carbadecaborate,

Tri (butyl) ammonium-1-carbadodecaborate,

Tri (butyl) ammonium-1-trimethylsilyl-1-carbadecaborate,

Tri (butyl) ammonium bis (nonahydrid-1,3-dicarbonnonaborate) cobaltate (III),

Tri (butyl) ammonium bis (undecahydrid-7,8-dicarbaundecaborate) ferrate (III) of importance.

Combinations of at least one of the amines mentioned above and a support with organic compounds as described in patent WO 99/40129 are also important as cocatalyst systems.

The preferred constituent of these cocatalyst systems are the compounds of the formulas (A) and (B),

wherein

P 7 is a hydrogen atom, a halogen atom, a C-ι-C o-koh! Enstoffha! Tige

Group, in particular C ₁ -C ₂₀ alkyl, -C-C ₂₀ haloalkyl, d-Cio-alkoxy, C ₆ - C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄ o-arylalkyl, C ₇ -C ₄₀ -

Halogenarylalkyl, C ₇ -C o -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl. R ¹⁷ can also be a -OSiR ¹⁸ ₃ group, in which R ^{18 are} identical or different and have the same meaning as R ¹⁷ .

In addition, further preferred cocatalysts are generally 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 ⁸⁰ ) s (C)

R ¹⁷ ₂ BX ¹ -BR ¹⁷ ₂ (D)

R ¹⁷

.B, O ^{'^} O

^^ O ^^ R ¹⁷

(E)

(F)

wherein

R ⁸⁰ is a hydrogen atom or a boron-free Cι-C ₄₀ -group such as Cι-C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₄₀ -Arylalky, C -C ₄₀ -alkylaryl may be, and wherein

R1 has the same meaning as above,

X ¹ is an element of VI. Main group of the Periodic Table of the Elements or an NR group, in which R is a hydrogen atom or a C ₁ -C ₂ -hydrocarbon radical such as C 1 -C ₂₀ alkyl or C 1 -C ₂₀ aryl, D is an element of VI. Main group of the Periodic Table of the Elements or an NR group, in which R is a hydrogen atom or a CrC ₂ o hydrocarbon radical such as -CC ₂₀ alkyl or C ₁ -C ₂₀ aryl, v is an integer from 0 to 3, s is a is an integer from 0 to 3, h is an integer from 1 to 10,

B is boron,

AI is aluminum.

If appropriate, the elemental organic compounds are combined with an organometallic compound of the formula III to V and or VII [M ^ 0R ^^, where M ^ 0 is an element of I., II. And III. Main group of the Periodic Table of the Elements is, R19 is the same or different and is a hydrogen atom, a halogen atom, a C- | -C4o-carbon-containing group, in particular C- | -C2fj- alkyl-, C6-C40-A17I-, C7-C4o- Aryl-alkyl or C7-C4o-alkyl-aryl 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 H ₃ OC-

The organometallic compounds of the formula VII are preferably neutral Lewis acids in which M ^ O is lithium, magnesium and / or aluminum, in particular aluminum. Examples of the preferred organometallic compounds of the formula XII are trimethylaluminium, triethylaluminium, triisopropylaluminum, trihexylaluminium, trioctylaluminium, tri-n-butylaluminium, trin-propylaluminium, triisoprenaluminium, dimethylaluminium monochloride, diethylaluminiumaluminiumchloromethylaluminium chloride, diethylaluminiumaluminium chloride, , Dimethylaluminiumhydrid, Diethylaluminiumhydrid, Diisopropylaluminiumhydrid, Dimethylaluminium (trimethylsiloxid), Dimethylaluminium (triethylsiloxid), Phenylalan, Pentafluorphenylalan and o-Tolylalan.

Further cocatalysts which may be unsupported or supported are those in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A-824112, EP-A-824113, EP-A-811627, W097 / 11775 and DE-A-19606167 compounds to use.

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

Polyolefins).

Suitable inorganic oxides can be found in the II-VI main group of the periodic table and the III-IV sub-group in the periodic table of the elements. Examples of oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures, and hydrotalcites. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, ZrO ₂ , Ti0 ₂ or B ₂ 0 ₃ , to name just a few. The carrier materials used have a specific surface area 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 from 1 to 500 μm. Carriers with a specific surface area 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 has a naturally low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as with the use of silica gel as a carrier material, dehydration or drying is recommended. The thermal dehydration or drying of the carrier material can be carried out under vacuum and at the same time with an inert gas blanket (eg nitrogen). The drying temperature is 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. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.

Dehydration or drying of the carrier material is also possible chemically by reacting the adsorbed water and the hydroxyl groups on the surface with suitable inerting agents. Through the reaction with the inerting reagent, the hydroxyl groups can be completely or partially converted into a form which does not lead to any negative interaction with the catalytically active centers. Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane, or organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium. The chemical dehydration or inertization of the carrier material takes place, for example, by suspending the carrier material in a suitable manner with the exclusion of air and moisture Solvent with the inerting reagent in pure form or dissolved in a suitable solvent to react. Suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene. The inerting takes place at temperatures 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 to 5 hours. After the chemical dehydration has ended, the support material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then in an inert gas stream or on

Vacuum dried.

Organic carrier materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be freed of adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.

To prepare the supported catalyst system, at least one of the transition metal compounds of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.

The preparation so obtained is then mixed with the dehydrated or rendered inert support material, the solvent removed and the resulting supported transition metal compound catalyst system dried to ensure that all or most of the solvent is removed from the pores of the support material. The supported catalyst is obtained as a free flowing powder. A process for the preparation of 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, the transition metal compound component having one of the structures described above, b) application of the Transition metal compound / cocatalyst mixture on a porous, preferably inorganic, dehydrated support c) removing the majority of the solvent from the resulting mixture d) isolating the supported catalyst system e) optionally prepolymerizing the resulting supported catalyst system with one or more olefinic monomer (s) to obtain a prepolymerized supported catalyst system.

Preferred solvents for the preparation of the transition metal compound / cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve. However, the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of transition metal compound and cocatalyst components is soluble in the solvent selected. Examples of suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene.

Toluene is very particularly preferred.

The amounts of aluminoxane and transition metal compound used in the preparation of the supported catalyst system can be varied over a wide range. A molar ratio of aluminum to the transition metal in the transition metal compounds of 10: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 50: 1 to 500: 1. In the case of methylaluminoxaή, 30% toluene solutions are preferably used; the use of 10% solutions is also possible. For preactivation, the transition metal compound is dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the transition metal compound separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Toluene is preferably used. The preactivation time is 1 minute to 200 hours. The preactivation can take place at room temperature (25 ° C). In individual cases, the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity. In this case, a higher temperature means a range between 50 and 100 ° C. The preactivated solution or the transition metal compound / cocatalyst mixture is then combined with an inert support material, usually silica gel, which is in the form of a dry powder or as a suspension in one of the abovementioned solvents. The carrier material is preferably used as a powder. The order of addition is arbitrary. The pre-activated

Transition metal compound-cocatalyst solution or the transition metal compound-cocatalyst mixture can be metered into the support material provided, or the support material can be introduced into the solution presented. The volume of the pre-activated solution or the transition metal compound -

Cocatalyst mixture can 100% of the total pore volume of the used

Exceed carrier material or up to 100% of the total pore volume.

The temperature at which the preactivated solution or the transition metal compound-cocatalyst mixture with the support material in

Contact can vary between 0 and 100 ° C. However, lower or higher temperatures are also possible.

The solvent is then completely or largely removed from the supported catalyst system, and the mixture can be stirred and optionally also heated. Both the visible portion of the solvent and the portion in the pores of the carrier material are preferably removed. The solvent can be removed in a conventional manner using vacuum and / or purging with inert gas. During the drying process, the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 ° C. The free solvent is the visible proportion of solvent in the mixture. Residual solvent is the proportion that is enclosed in the pores. As an alternative to a complete removal of the solvent, the supported catalyst system can also be dried only to a certain residual solvent content, the free solvent having been removed completely. The supported catalyst system can then be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again. The supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before it is used in a polymerization process. The prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.

As an additive, a small amount of an olefin, preferably an olefin (for example vinylcyclohexane, styrene or phenyldimethylvinylsilane) can be added as a modifying component or an antistatic (as described in US Serial No. 08/365280) during or after the preparation of the supported catalyst system. The molar ratio of additive to non-

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 process for the preparation of a polyolefin by polymerization of one or more olefins in the presence of the catalyst system according to the invention, comprising at least one transition metal component of the formula VII. The term polymerization is understood to mean homopolymerization and also copolymerization.

Olefins of the formula R _m -CH = CH-R _n are preferably polymerized, in which R _m and R _{n are} identical or different and denote a hydrogen atom or a carbon-containing radical having 1 to 20 C atoms, in particular 1 to 10 C atoms , 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, preferably 2 to 10 C -

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, tetracyclododecene or methyl norbornene. Ethene or propene are preferably homopolymerized in the process according to the invention, or propene with ethene and / or with one or more 1-olefins having 4 to 20 carbon atoms, such as butene, hexene, styrene or vinylcyclohexane, and / or one or more dienes 4 to 20 carbon atoms, such as 1, 4-butadiene, norbomadiene, ethylidene norbones or ethyl norbornadiene, copolymerized. Examples of such copolymers are ethene / propene copolymers, ethene / norbornene, ethene / styrene or ethene / propene / 1,4-hexadiene terpolymers. The polymerization is carried out at a temperature of 0 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 50 to 80 ° C. The pressure is 0.5 to 2000 bar, preferably 5 to 64 bar.

The polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages. The catalyst system shown according to the invention can be used as the only catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably in combination with at least one

Alkyl compound of the elements from I. to III. Main group of the periodic table, e.g. an aluminum, magnesium or lithium alkyl or an aluminoxane can be used. The alkyl compound is added to the monomer or suspending agent and is used to purify the monomer from substances which can impair the catalyst activity. The amount of the alkyl compound added depends on the quality of the monomers used. If necessary, hydrogen is added as a molecular weight regulator and / or to increase the activity. The catalyst system can be fed to the polymerization system neat or for better dosing with inert components such as paraffins, oils or

Waxing. In the polymerization, an antistatic can also be metered into the polymerization system together with or separately from the catalyst system used. The polymers represented by the catalyst system according to the invention have a uniform grain morphology and have no fine grain proportions. In the

Polymerization with the catalyst system according to the invention does not result in deposits or caking.

The invention is illustrated by the following examples which, however, do not restrict the invention.

General information: The production and handling of the organometallic compounds was carried out with the exclusion of air and moisture under an argon protective gas (Schlenk technique or glove box). All required solvents were flushed with argon before use and absoluteized using a molecular sieve. 1. Representation of the ligands

Example 1: frans-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1, 2-diamine

15.0 g (0.13 mol) of trans-, 2-diaminocyclohexane are in

80 ml of methanol are dissolved and 28.1 g (0.26 mol) of pyridine-2-aldehyde are added in portions at room temperature.

The solution is refluxed for an hour and then open

Cooled to room temperature. The precipitated solid is filtered off and dried in an oil pump vacuum. The product is obtained in the form of a light yellow powder with a yield of 23 g (79 mmol, 60%). ¹ H NMR (400

MHz, CDCI ₃ ): δ = 8.55 (m, 2H, Py), 8.31 (s, 2H, = CH), 7.88, 7.63, 7.21 (3 xm, 6H,

Py), 3.52 (m, 2H, NC-H), 1.90-1.49 (m, 8H, (CH ₂ ) ₄ ) ppm.

Example 2: fraπs-N, N'-bis-pyridin-2-yl-cyclohexan-1, 2-diamine

5 g (17 mmol) -ra / 7s-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1, 2-diamine are placed in 41 ml methanol and added in portions with stirring at room temperature with 1.35 g (35.7 mmol) Sodium borohydride added. When the addition is complete, it will

Reaction mixture refluxed for one hour. After cooling 30 ml of water are added to room temperature and the product is extracted with 3 × 100 ml of dichloromethane. The combined organic phases are dried over magnesium sulfate and that

Solvent is removed in vacuo, the product being obtained in the form of a slightly yellow oil in a yield of 5 g (16.9 mmol, 99%) and in a purity of 96% (according to GC). ¹ H-NMR (400 MHz, CDCI ₃ ): δ = 8.52, 7.62, 7.39, 7.14 (4 xm, 8H, Py), 4.03 (d, J = 14 Hz, 2H benzyl. CH ₂ ), 3.84 (d, J = 14 Hz, 2H benzyl. CH ₂ ), 2.50 (s, br, 2H, NH), 2.32 (m, 2H, NCH), 2.16 - 1.07 (m, 8H, (CH ₂ ) ₄ ) ppm. Example 3: N '- [2' - (Dimethylamino-methylenamino) - [1, 1 '] binaphthalenyl-2-yl] -N, N-dimethyl-formamidine

9.3 g (52.5 mmol) of 2-pyridinesulfonyl chloride are stirred in 175 ml of N, N-dimethylformamide for 5 min at room temperature.

Then 10 g (35 mmol) of 2,2'-diamino-1, 1 '- binaphthyl are added and 5 minutes at room temperature touched. The solvent is removed in vacuo and the brown residue is mixed with 100 ml of a 4M potassium carbonate solution and 200 ml of tert-butyl methyl ether. The aqueous phase is extracted 3 times with 100 ml of tert-butyl methyl ether, the combined organic

Phases are dried over magnesium sulfate, and the solvent is in

Vacuum removed. The crude product thus obtained is recrystallized from methanol, the desired product being obtained in the form of light yellow crystals with a yield of 10.3 g (74%, 26 mmol). ¹ H-NMR (400 MHz, CDCI ₃ ): δ = 7.71-

7.39 (m, 14 H, aromatic H, N = CH), 2.83 (s, 12H, CH ₃ ) ppm.

Example 4: N ^ N ^ -Bis-dimethylaminomethyl-fl'Ibinaphthalenyl- ^ '- diamine

5 g (12.6 mmol) of N '- [2' - (dimethylamino-methylenamino) - [1, 1 '] binaphthalenyl-2-yl] -N, N-dimethylformamidine in 80 ml of methanol are added

Room temperature 0.96 g (25.3 mmol) sodium borohydride added in portions. After the addition is complete the reaction mixture is refluxed for one hour.

After cooling to room temperature, 60 ml

Water is added and the product is extracted with 3 × 100 ml dichloromethane.

The combined organic phases are dried over magnesium sulfate and the solvent is removed in vacuo, the product being obtained in the form of a slightly yellow oil in a yield of 4.9 g (12.3 mmol, 98%) and in a purity of 97% (according to GC) becomes. ¹ H-NMR (400 MHz, CDCI ₃ ): δ = 7.55 - 6.82 (m, 12H, aromatic H), 4.13 (s, 4H, NHCH ₂ NMe ₂ ), 2.75 (s, br, 2H, NH), 2.27 (s, 12H, NMe ₂ ) ppm. Example 5: frans-N, N ^, -Bis- (2-diphenylphosphanyl-benzylidene) -cyclohexane-1,2-diamine

7.5 g of granular molecular sieve (4A) are baked out in a Schlenk tube. After adding 50 ml

Dichloromethane, 1.75 g (15 mmol) trans-1, 2-diaminocyclohexane and 8.7 g (30 mmol) o-diphenyl- phosphinobenzaldehyde, the reaction mixture is stirred for 24 h. After filtration through Celite, the solvent is removed and the residue is recrystallized from 50 ml of ethanol, the

Product with a yield of 8.6 g (13 mmol, 87%) is obtained in the form of a light yellow powder. ¹ H-NMR (400 MHz, CDCI ₃ ): δ = 8.71 (d, J = 4 Hz, 2H, N = CH), 7.78 - 6.64 (m, 28 H, aromatic H), 3.16 (m, 2H, CH), 1.66-1.31 (m, 8H, (CH ₂ ) ₄ ) ppm.

Example 6: fra / 7s-N, N'-bis (2-diphenylphosphanyl-benzyl) cyclohexane-1,2-diamine

A solution of 3.30 g (5.0 mmol) of fraA7s-N, N'-bis- (2-diphenylphosphanyl-benzylidene) -cyclohexane-1,2-diamine in 60 ml of methanol is mixed with 1.14 g (30 mmol) of sodium borohydride in portions. The solution is refluxed for 24 h and after cooling to room temperature with 20 ml of water are added. The organic phase is extracted 3 times with 50 ml of dichloromethane and the combined organic phases are extracted 2 times with 30 ml of 10% ammonium chloride.

Washed solution and 30 ml of water. After drying over magnesium sulfate, the solvent is removed in vacuo and the residue is recrystallized from 30 ml of ethanol. The product precipitates in the form of light yellow crystals with a yield of 2.68 g (4.0 mmol, 80%). ¹ H-NMR (400 MHz, CDCI ₃ ): δ = 7.65 - 6.92 (m, 28 H, aromatic H), 4.1 1, 3.98 (2 xd, J = 13.4 Hz, 4 H, Ar-CH ₂ ), 2.21 (m, 2H, NCH), 1.63 -

1.27 (m, 8H, (CH ₂ ) ₄ ) ppm. 2. Presentation of the complexes

General information: All reactions were carried out under an Ar protective gas atmosphere. Some of the complexes shown are paramagnetic and therefore cannot be characterized by NMR spectroscopy.

Example 7: (fra / 7S-N ₅ N'-bis-pyridin-2-ylmethylene-cyclohexane-1,2-diamino) - iron (II) chloride

In a heated Schlenk tube, 1.0 g (3.4 mmol) of frans-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1, 2-diamine are dissolved in 40 ml of THF and 431 mg (3.4 mmol) of iron (II) chloride (wsfr.) added. After 0.5 h, the solution turns deep blue. After stirring for a further 2 h at room temperature Solvent removed in vacuo and the residue stirred with 10 ml of heptane. After filtration through a G3 frit, the product is obtained as a dark blue solid with a yield of 1.41 g (3.36 mmol, 99%).

Example 8: (frans-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1, 2-diamino) - nickel (II) bromide

In a heated Schlenk tube, 1.0 g (3.4 mmol) of fraπs-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1, 2-diamine are dissolved in 40 ml of THF and with 1.04 g (3.4 mmol) of nickel (II) bromid * DME offset. After 0.2 h the color changes

Solution dark. After stirring for a further 2 h at room temperature, the solvent is removed in vacuo and the residue was stirred with 10 ml of heptane. After filtration through a G3 frit, the product is obtained as a dark blue solid with a yield of 1.32 g (2.58 mmol, 76%). Example 9: (frans-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1, 2-diamino) palladium (II) chloride

In a heated Schlenk tube, 1.0 g (3.4 mmol) of ra? S-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1,2-dia are dissolved in 40 ml of THF and mixed with 882 mg (3.4 mmol)

Palladium (II) chloride * 2 CH ₃ CN added. After 0.2 h, the solution turns yellow. After stirring for a further 2 h

The room temperature is removed in vacuo and the residue is stirred with 10 ml of heptane. To

Filtration through a G3 frit gives the product in a yield of 1.45 g (2.92 mmol, 86%) as a yellow solid.

Example 10: (N ^, - [2 ^, - (Dimethylamino-methylenamino) - [1,1 '] binaphthalenyl-2-yl] - N, N-dimethyl-formamidino) -iron (II) chloride

In a heated Schlenk tube, 1.0 g (2.5 mmol) of N '- [2 ^, - (Dimethylamino-methylenamino) - [1, 1' jbinaphthalenyl-2-yl] -N, N-dimethyl-formamidine are dissolved in 40 ml of THF and mixed with 317 mg (2.5 mmol) of iron (II) chloride (white).

After 0.5 h, the solution turns deep blue. After another

2 h of stirring at room temperature, the solvent in

Vacuum removed and the residue stirred with 10 ml of heptane. After filtration through a G3 frit, the product is obtained as a dark blue solid with a yield of 1.01 g (1.9 mmol, 78%).

Example 11: (N'-P '^ Dimethylamino-methylenaminoJ-fl, 1'] binaphthalenyl-2-yl] - N, N-dimethyl-formamidino) -nickel (II) bromide

In a heated Schlenk tube, 1.0 g

(2.5 mmol) N '- [2 ^, - (dimethylamino-methylene-amino) - [1, 1'] binaphthalenyl-2-yl] -N, N-dimethylformamidine dissolved in 40 ml THF and with 772 mg (2.5 mmol) of nickel (II) bromide * DME added. After 0.2 h the solution turns dark. After stirring for a further 2 h at room temperature, the solvent is removed in vacuo and the residue is stirred with 10 ml of heptane. After filtration through a G3 frit, the product is obtained as a dark blue solid with a yield of 1.17 g (1.9 mmol, 76%).

Example 12: (N'-P dimethylamino-methylenaminoJ-II 'jbinaphthalenyl ^ -yl] - N, N-dimethyl-formamidino) palladium (II) chloride

In a heated Schlenk tube, 1.0 g (2.5 mmol) of N '- [2' - (Dimethylamino-ethylenamino) - [1, 1 'jbinaphthalenyl-2-yl] -N, N-dimethyl-formamidine are dissolved in 40 ml of THF and with 649 mg (2.5 mmol) palladium (II) chloride * 2 CH ₃ CN added. After 0.2 h, the solution turns yellow. After stirring for a further 2 h at room temperature

Solvent removed in vacuo and the residue stirred with 10 ml of heptane.

After filtration through a G3 frit, the product is obtained with a yield of 1.45 g

(2.48 mmol, 99%) obtained as a yellow solid.

Example 13: (frans-N, N'-bis (2-diphenylphosphanyl-benzylidene) -cyclohexane-1,2-diamino) -iron (II) chloride

In a heated Schlenk tube, 1.0 g (1.5 mmol) -rar? SN, N'-bis- (2-diphenylphosphanyl-benzylidene) -cyclohexane-1, 2-diamine are dissolved in 40 ml THF and with 190 mg (1.5 mmol) iron (II) chiorid

(whs.) offset. The solution changes color after 0.5 h deep blue. After stirring for a further 2 h at room temperature, the solvent is removed in vacuo and the residue is stirred with 10 ml of heptane. After filtration through a G3

Frit, the product is obtained with a yield of 0.98 g (1.2 mmol, 83%) as a dark blue solid. Example 14: (fra / 7S-N, N ^, -Bis- (2-diphenylphosphanyl-benzylidene) -cyclohexane-1,2-diamino) -nickel (II) bromide

In a heated Schlenk tube, 1.0 g (1.5 mmol) of ra / 7s-N, N'-bis- (2-diphenylphosphanyl-benzylidene) -cyc! Ohexane-1, 2-diamine are dissolved in 40 ml of THF and mixed with 463 mg (1.5 mmol) of nickel (II) bromide * DME added. After 0.2 h the solution turns dark.

After stirring for a further 2 h at room temperature

Solvent removed in vacuo and the residue stirred with 10 ml of heptane.

After filtration through a G3 frit, the product is obtained with a yield of 1.22 g

(1.4 mmol, 93%) obtained as a dark blue solid.

Example 15: (franst, N'-Bi ^ -diphenylphosphanyl-benzylidene-J-cyclohexane-1,2-diamino) -palladium (II) chloride

In a heated Schlenk tube, 1.0 g (1.5 mmol) of fr? SN, N'-bis- (2-diphenylphosphanyl-benzylidene) -cyclohexane-1,2-diamine are dissolved in 40 ml of THF and mixed with 389 mg (1.5 mmol) Palladium (II) chloride * 2 CH ₃ CN added. After 0.2 h, the solution turns yellow.

After stirring for a further 2 h at room temperature

Solvent removed in vacuo and the residue stirred with 10 ml of heptane. After filtration through a G3 frit, the product is obtained as a yellow solid with a yield of 1.03 g (1.2 mmol, 82%).

Example 16: (fraπs-N, N'-bis-pyridin-2-ylmethylene-cyclohexan-1, 2-diamido) - dibenzylzircon

1.0 g (3.4 mmol) -rans-N, N'-bis-pyridin-2-yl-cyclohexan-1, 2-diamine in 20 ml toluene / THF 10: 1 are placed in a heated Schlenk tube and at -30 ° C. with a solution of 1.5 g (3.4 mmol) of tetrabenzyl zirconium in 10 ml of toluene are added. After the addition is complete, the mixture is stirred for a further 1 h at -30 ° C. and overnight at room temperature. The solvent is evaporated down to 7 ml and the solution is stored at -30 ° C. overnight. The precipitate thus obtained is isolated by filtration through a G4 frit and dried in an oil pump vacuum. The product is obtained in the form of a powder with a yield of 0.89 g (1.57 mmol, 46%). ¹ H-NMR (CDCI ₃ , 400 MHz): δ = 8.61 - 6.92 (m, 18H, Py, aromatic H), 4.72, 4.03 (2 xm, J, 2H benzyl. NCH ₂ ), 3.88 (m, 2H , NCH), 2.26-1.13 (m, 12H, ZrCH ₂ , (CH ₂ ) ₄ ) ppm.

Example 17: (N ² , N ² '-Bis-dimethylaminomethyl- [1,1 ^, ] binaphthalenyl-2,2'-diamido) -dibenzylzircon

1.0 g (2.5 mmol) of N ² , N'-bis-dimethylaminomethyl- [1, 1 '] binaphthalene-2,2'-diamine in 20 ml of toluene / THF 10: 1 are placed in a heated Schlenk tube and at - 30 ° C with a solution of 1.14 g (2.5 mmol) of tetrabenzylzircon in 10 ml of toluene. After the addition is complete, the mixture is still at -30 ° C and above for 1 h

Stirred at room temperature overnight. The solvent is evaporated down to 11 ml and the solution is stored at -30 ° C. overnight. The precipitate thus obtained is isolated by filtration through a G4 frit and dried in an oil pump vacuum. The product is obtained in the form of a powder with a yield of 1.01 g (1.5 mmol, 60%). ¹ H-NMR (CDCI ₃ , 400 MHz): δ = 7.95 - 6.81 (m, 22H, aromatic H), 4.32 (m, 4H, NCH ₂ ), 2.73 (s, 12H, CH ₃ ), 1.25 (s , 4H, ZrCH ₂ ) ppm.

Example 18: (fra / 7S-N, N'-bis (2-diphenylphosphanyl-benzyl) cyclohexane-1,2-diamido) ~ dichlorozircon

In e mm cycl and Toluene). It is stirred overnight at room temperature and then 704 mg (3.0 mmol) of zirconium tetrachloride are added. After stirring for five hours at room temperature, the solvent is removed in vacuo. The residue is stirred with 20 ml of dichloromethane and filtered through Celite. The solvent is removed, the crude product thus obtained is recrystallized from 10 ml of a toluene / heptane 7: 3. and isolated by filtration through a G4 frit with a yield of 1.87 g in the form of a gray powder. ¹ H-NMR (CDCI ₃ , 400 MHz): δ = 8.11 - 6.89 (m, 28 H, aromatic H), 3.69 (s, 4H, NCH ₂ ), 3.11 (m, 2H, NCH), 1.43 - 0.99 (m, 8H, (CH ₂ ) ₄ ) ppm.

Claims

claims

1. Compounds of formula I.

Formula I wherein M ^{1 is} a metal of III. to XII. Group of the Periodic Table of the Elements, in particular Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd or Cu and D ^{1 is the} same or different and a donor atom of the XV and XVI. Group of

Periodic table of the elements, in particular N, P, As, O, S, Se and Te and D ^{2 is the} same or different and a donor atom of XV. and XVI. Group of the Periodic Table of the Elements, in particular N, P, As, O, S, Se and Te, and

Z is a bridging structural element between the two donor atoms D ¹ and X is the same or different and a hydrogen atom, a C ₁ -C10-

Hydrocarbon group such as Ci-C-io-alkyl, Ce-Cio-aryl, C ₇ -C _2u alkylaryl, C ₇ - C ₂₀ arylalkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl or a halogen atom , or OR ⁶ ,

SR ^δ , OS0 ₂ R ⁶ , OSi (R ⁶ ) ₃ , Si (R ⁶ ) ₃ , P (R ⁶ ) ₂ , P (R ⁶ ) ₃ , NCR ⁶ , N (R ⁶ ) ₃ , B (R ⁶ ) ₄ , substituted or unsubstituted pyridine or N (R ⁶ ) ₂ , and R ^{1 is the} same or different and is a hydrogen atom, a CrC ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₂ o- alkylaryl group, a C ₇ -C ₃₀ - aralkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group or a halogen-containing CrC ^ alkyl, C ₆ -C ₂₀ aryl group, C ₇ -C ₂₀ - Aikylarylgruppe, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ - alkynyl group or a heteroatom-containing Cι-C ₂₀ alkyl, C ₆ -C ₂₀ - Aryl group, C ₇ -C ₂₀ -alkylaryl, C ₇ -C ₃ O-arylalkyl group, C ₂ -C ₂₀ - alkenyl, C ₂ -C ₂₀ alkynyl group, or Si (R ⁶⁾ _3, wherein one or more residues R ¹ with one or more radicals R a mono- or polycyclic ring system ^2, can such as pyridinyl, quinolinyl or isoquinolinyl form, which may itself be substituted by one or more radicals R ^6, and R ² is the same or different and are a hydrogen atom, -C-C n-alkyl group, a C ₆ -C ₂ o-aryl group, a C7-C ₂₀ -alkylaryl group, a C7-C ₃₀ -arylalkyl group, a C ₂ -C ₂ o-alkenyl group, a C ₂ -C ₂ o -Alkynyl group or a halogen-containing -C _2u -alkyl group, C6-C ₂₀ -aryl group, C ₇ -C ₂ o-

Alkylaryl, C7-C ₃₀ arylalkyl group, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ - alkynyl group or a heteroatom-containing Cι-C ₂ o alkyl group, C ₆ -C ₂₀ - aryl group, C7-C ₂₀ alkylaryl group, C ₇ -C ₃ o-arylalkyl group, C ₂ -C ₂ o-alkenyl group, C ₂ -C ₂₀ alkynyl group or Si (R ⁶ ) ₃ , where one or more radicals R ² with one or more radicals R ¹ and / or R ^{3 can form} a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or isoquinolinyl, which in turn can be substituted by one or more radicals R ⁶ , and R ^{3 is the} same or different and a hydrogen atom, a C 1 -C ₂₀ -Alkyl group, a C ₆ -C ₂₀ -aryl group, a C ₇ -C ₂₀ -alkylaryl group, a C ₇ -C ₃ o-

Arylalkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group or a halogen-containing group C6-C ₂₀ aryl group, C ₇ -C ₂ o-alkylaryl, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ - alkynyl group or a heteroatom-containing CrC ₂₀ alkyl, C ₆ -C ₂₀ - aryl group, C -C ₂₀ alkylaryl group, C ₇ -C ₃ o-arylalkyl group, C ₂ -C ₂₀ -

Alkenyl group, C ₂ -C ₂ o-alkynyl group or Si (R ⁶ ) ₃ means, where one or more radicals R ³ with one or more radicals R ^{2 can form} a mono- or polycyclic ring system, such as pyridinyl, quinolinyl or isoquinolinyl , which in turn can be substituted by one or more radicals R ^δ , and

R ^{4 is the} same or different and is a hydrogen atom, a -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₂₀ alkylaryl group, a C ₇ -C ₃₀ arylalkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group or a halogen-containing C ₁ -C ₂ o -alkyl group, C6-C ₂₀ aryl group, C ₇ -C ₂₀ - Alkylaryl, C7-C ₃₀ arylalkyl group, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂ RJ alkynyl group or a heteroatom-containing Cι-C ₂ o alkyl group, C ₆ -C ₂₀ - aryl group, C7-C _2u - Is alkylaryl group, C ₇ -C ₃ o-arylalkyl group, C ₂ -C ₂₀ alkenyl group or C ₂ -C ₂ o-alkynyl group, and R ^{5 are the} same or different and a hydrogen atom, a -C-C ₂₀ -

! Alkyl group, a C6-C ₂₀ -Ary group, a C ₇ -C ₂ o-alkylaryl group, a C ₇ -C ₃₀ - aralkyl group, a C ₂ -C ₂ o-alkenyl group, a C ₂ -C ₂₀ alkynyl, or a halogen-containing -C ₂ o -alkyl group, C6-C ₂₀ aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂ o-alkynyl group or a heteroatom-containing Cι-C ₂₀ alkyl, C ₆ -C ₂₀ -

Aryl, C7-C ₂₀ alkylaryl, C ₇ -C ₃ O-arylalkyl group, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂ o-alkynyl group, where a plurality of radicals R ⁵ to each other form a mono- or polycyclic ring system can, and

R ^{6 are the} same or different and are a hydrogen atom, a halogen atom, a C1-C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₂ o-alkylaryl group, a

C ₇ -C ₃₀ arylalkyl group, a C ₂ -C ₂ o-alkenyl group, a C ₂ -C ₂₀ alkynyl group or a halogen-containing Cι-C ₂ o alkyl group, C ₆ -C ₂ o-aryl, C ₇ -C ₂ o- alkylaryl, C ₇ -C ₃₀ arylalkyl group, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂₀ - alkynyl group or a heteroatom-containing Cι-C ₂ o alkyl group, C ₆ -C ₂₀ - aryl, C7- C ₂₀ alkylaryl group, C ₇ -C ₃ o-arylalkyl group, C ₂ -C ₂ o-

Alkenyl group, C ₂ -C ₂ o-alkynyl group, and a are each the same or different and represent an integer from 1 to 10 and b are each the same or different and represent an integer from 0 to 3 and c each is the same or different and are an integer from 0 to 2 and d are each the same or different and are an integer from 0 to 2 and e are each the same or different and are an integer from 0 to 2 and f are each the same or different and is an integer from 2 to 20 and g is the same or different and 1 or 2 is and h are each the same or different and represent an integer from 1 to 4 and i are each identical or different and represent an integer from 0 to 24 and j are each identical or different and represent an integer from 0 to 10, with the Provided that complexes in which Z _a (R ⁵ ) _{f is} unsubstituted or substituted ethyl, and D ¹ is nitrogen, R ³ is hydrogen, d is 1 and two R ² together form a substituted benzene ring which can be substituted by D ² is oxygen substituted, so-called salen complexes are excluded from the invention.

2. Compounds according to claim 1, characterized in that

M ^{1 is} Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd or Cu and D ^{1 is the} same or different and N, P, As, O, S, Se and Te is and

D ^{2 is the} same or different and is N, P, As, O, S, Se and Te.

Compounds according to claim 1 or 2, characterized in that D ¹ -Z ¹ (R ⁵ ) _f -D ¹ for a structure selected from the group IIIa to Hz

ll a II b II c II d H e II f ιι g II h II i

II j II k IM U m II n II o

II u II v II w II x H y

Formula II a - z is in which the radicals Dvm R and i have the meaning given in claim 1.

4. Compounds according to claim 1 to 3, characterized in that a are each the same or different and mean an integer from 1 to 4 and b are each the same or different and mean an integer from 0 to 2 and c each is the same or different and are an integer from 0 to 2 and d are each the same or different and are an integer from 0 to 2 and e are each the same or different and are an integer from 0 to 2 and f are each the same or different and are an integer from 2 to 20 and g are each the same or different and 1 or 2 and h are each the same or different and are an integer from 1 to 4 and i are each the same or different and an integer from 0 to 24 and j are the same or different and represent an integer from 0 to 10.

5. Compounds according to claim 1 to 4, characterized in that M ^{1 is} Ti, Zr, Hf, Fe, Co, Ni or Pd and

D ^{1 is the} same or different and is N, P, O and S, and D ^{2 is the} same or different and N, P, O and S, is and

Z corresponds to the formulas II d, II j, II o, II r or 11 s defined in claim 3 and

X is the same or different and means chloride, bromide, iodide, methyl, ethyl, propyl, ethenyl, propinyl, phenyl, benzyl, methoxy, trifluoromethanesulfonyl, dimethylamido, tetrafluoroborate, triphenylphophine, acetonitrile, trimethylsilyl or pyridine, and

R ^{1 is} identical or different and represents a hydrogen atom, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, or a radical R ¹ with a radical R ^{2 is} a mono- or polycyclic Ring system forms, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn can be substituted by one or more radicals R ⁶ , and R ^{2 is the} same or different and is a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, or a radical R ² with a radical R ^{1 is} a mono- or polycyclic

Ring system forms, preferably pyridinyl, quinolinyl or isoquinolinyl, which in turn can be substituted by one or more radicals R ⁶ , and R ^{3 is the} same or different and is a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, and

R ^{4, the} same or different, is a hydrogen atom, methyl, ethyl, propyl, i-

Propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, and R ^{5 is the} same or different and is a hydrogen atom, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert- Means butyldimethylsilyl, or where several radicals R ⁵ can form a mono- or polycyclic ring system with one another, and R ^{6 is} identical or different and is a hydrogen atom, fluorine, chlorine, bromine, iodine,

Is methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or tert-butyldimethylsilyl, and a is the same or different and 1 or 2 and b is the same or different and an integer of 0 to 2 and c are the same or different and are an integer from 0 to 2 and d are each the same or different and are an integer from 0 to 2 and e are each the same or different and 0 or 1 and f are each are identical or different and represent an integer from 2 to 20 and g are each identical or different and represent 1 or 2 and h are each identical or different and represent an integer from 1 to 4 and i are each the same or different and represent an integer from 0 to 18 and j are each identical or different and represent an integer of 0 to 6.

6. A catalyst system containing at least one compound according to claims 1 to 5 and at least one cocatalyst.

7. A catalyst system containing at least one compound according to claims 1 to 5 and at least one carrier.

8. Use of the catalyst system according to claim 6 and / or 7 for the polymerization of one or more olefins of the formula Rm-CH = CH-R _n wherein 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, and R _m and R _n together with the atoms connecting them can form one or more rings.

9. A process for the polymerization of one or more olefins of the formula R _m -CH = CH-R _n wherein R _m and R _{n are the} same or different and one

Hydrogen atom or a carbon-containing radical having 1 to 20 carbon atoms, in particular 1 to 10 carbon atoms, and R _m and R _n together with the atoms connecting them can form one or more rings, in the presence of a catalyst system according to claim 6 and / or 7.