EP1373284A1 - Catalysts characterized by a donor-acceptor interaction - Google Patents

Abstract

The invention relates to compounds in which a transition metal is complexed with two ligand systems and the two systems are reversibly interlinked by at least one bridge from a donor and an acceptor, and at least one substituent on the acceptor group is a fluorinated aryl group. The invention also relates to the use of the inventive compounds as catalysts and to a method for polymerizing olefins.

Description

Catalysts with a donor – acceptor interaction

The present invention relates to compounds in which a transition metal is complexed with two ligand systems and the two systems are reversibly connected to one another by at least one bridge consisting of a donor and an acceptor, at least one substituent on the acceptor group being a fluorinated aryl radical, the use of these compounds as catalysts and a process for the polymerization of olefins.

The coordinative bond between the donor atom and the acceptor atom creates a positive (partial) charge in the donor group and a negative (partial) charge in the acceptor group:

Δ + Δ- [donor group - acceptor group]

The invention further relates to the use of these catalysts with a donor-acceptor interaction as polymerization catalysts.

Metallocenes as π complex compounds and their use as catalysts in the

Polymerization of olefms have long been known (EP-A-129 368 and the literature cited therein). It is also known from EP-A-129 368 that metallocenes in combination with aluminum alkyl / water as cocatalysts are effective systems for the polymerization of ethylene (for example, methylaluminoxane = MAO is formed from about 1 mol of trimethylaluminum and 1 mol of water). Other stoichiometric ratios have already been used successfully (WO 94/20506)). Metallocenes whose cyclopentadienyl skeletons are covalently linked to one another by a bridge are also already known. An example of the numerous patents and applications in this field is EP-A 704461, in which the linking group mentioned therein contains a (substituted) methylene group or ethylene group, a silylene group, a substituted silylene group, a substituted one Germylene group or a substituted phosphine group. The bridged metallocenes are also provided as polymerization catalysts for olefins in EP-A 704461.

Catalysts with a donor-acceptor interaction and their use as

Polymerization catalysts are known in principle.

For example, WO-A-98/01455 describes compounds in which a transition metal is complexed with two π systems, in particular with aromatic π systems (metallocenes), and the two systems by at least one bridge from one

Donor and an acceptor are reversibly connected to one another, the donor or acceptor atoms being bound as substituents on the π systems, and their use as polymerization catalysts.

WO-A-98/45339 describes compounds in which a transition metal with two π-

Systems, in particular complexed with aromatic π systems (metallocenes) and the two systems are reversibly connected to one another by at least one bridge consisting of a donor and an acceptor, at least one of the donor and acceptor atoms being part of the respective π system is, and their use as polymerization catalysts.

Patent applications WO-A-98/01483 to WO-A-98/01487 describe technical polymerization processes using the described catalysts with donor-acceptor interaction.

It is known from these documents that the catalysts with donor-acceptor interaction can advantageously be used as catalysts for olefin polymerization. However, it was surprising for the person skilled in the art that particularly advantageous catalysts with donor-acceptor interaction can be produced if one selects special substitution patterns on the acceptor group.

The invention thus relates to transition metal compounds with two π systems and at least one donor-acceptor interaction between these π systems, characterized in that these transition metal compounds have at least one fluorine-substituted aryl group on at least one acceptor atom.

Π systems according to the invention are substituted and unsubstituted ethylene, allyl, pentadienyl, benzyl, butadiene, benzene, the cyclopentadienyl anion and the species resulting from the replacement of at least one C atom by a heteroatom. Among the species mentioned, the cyclic ones are preferred. The type of coordination of such ligands (π systems) to the metal can be of the σ type or of the π type.

The transition metal compounds described in the applications WO-A-98/01455, WO-A-98/45339, WO-A-98/01483 to WO-A-98/01487 are also suitable as transition metal compounds with at least one donor-acceptor interaction Donor-acceptor interaction, characterized in that these transition metal compounds have fluorine-substituted aryl groups on the acceptor group.

Metallocene compounds of the formula are particularly suitable

(la) (! b),

in the

Cpl and Cpll represent two identical or different carbanions with a cyclopentadienyl-containing structure, in which one to all H atoms by identical or different radicals from the group of linear or branched C ₁ -C ₂₀ alkyl, the 1-fold to complete can be substituted by halogen, 1-3 times by phenyl and 1-3 times by vinyl, C ₆ -C ₁₂ aryl, haloaryl having 6 to 12 C atoms, organometallic substituents such as silyl, trimethylsilyl, ferrocenyl and 1- or Can be substituted twice by D and A.

D represents a donor atom which can additionally carry substituents and which has at least one fine electron pair in its respective bond state,

A denotes an acceptor atom which bears at least one fluorine-substituted aryl group, but preferably exclusively fluorine-substituted aryl groups, and which has an electron pair gap in its respective bond state,

where D and A are linked by a reversible coordinative bond in such a way that the donor group assumes a positive (partial) charge and the acceptor group a negative (partial) charge,

M for a metal from groups 3-7 of the Periodic Table of the Elements

IUPAC (1985) including the lanthanides and actinides, X represents an anion equivalent and

n means the number zero, one, two, three or four depending on the charge of M.

The first and second carbanions Cpl and Cpll with a cyclopentadienyl skeleton can be the same or different. The cyclopentadienyl skeleton can be, for example, one from the group of cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene, with fluorene and substituted fluorene being particularly preferred. Substituents 1 to 4 per cyclopentadiene or fused benzene ring may be mentioned. These substituents can be C ₁ -C ₂ o-alkyl, such as methyl, ethyl, propyl, isopropyl, butyl or iso-butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, eicosyl, C ₁ -C ₂ o-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, hexoxy, octyloxy,

Decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, halogen, such as fluorine, chlorine or bromine, C ₆ -C ₁₂ aryl, such as phenyl, C ₁ -C ₄ alkylphenyl, such as tolyl, ethylphenyl, (i-) propylphenyl , (i- / tert.) Butylphenyl, xylyl, halophenyl, such as fluoro-, chloro-, bromophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, pentachlorophenyl, naphthyl or biphenylyl, triorganylsilyl, such as trimethylsilyl (TMS ), Ferrocenyl and D or A as defined above. Fused aromatic rings can also be partially or fully hydrogenated, so that only the double bond remains, in which both the fused ring and the cyclopentadiene ring have a share. Furthermore, benzene rings, as in indene or fluorene, can contain one or two further fused benzene rings. Furthermore, the cyclopentadiene or cyclopentadienyl ring and a fused-on benzene ring can together contain a further fused benzene ring. Such cyclopentadiene skeletons are excellent ligands for transition metals in the form of their anions, each cyclopentadienyl carbanion of the optionally substituted form mentioned compensating for a positive charge of the central metal in the complex. Individual examples of such carbanions are: cyclopentadienyl, methyl-cyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, indenyl, phenylindenyl, 1,2-diethyl-cyclopentadienyl, tetramethyl-cyclopentadienyl, ethyl-cyclopentadienyl, n-butyl-cyclopentadienyl, n-octyl-cyclopentadienyl, ß-phenyl-propyl-cyclopentadienyl, tetrahydroindenyl, propyl-cyclopentadienyl, t-butyl-cyclopentadienyl, benzyl-cyclopentadienyl, diphenylmethyl-cyclopentadienyl, trimethylopentadienyl, tri-methylgannadyl Trifluoromethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, pentamethylcyclopentadienyl, fluorenyl, tetrahydro- or octahydro-fluorenyl, benzo-fused fluorenyls and indenyls, N, N-dimethylamino-cyclopentadienyl, dimethylphosphino-cycladentyl-dienyl N-dimethylaminomethyl) -cyclopentadienyl.

Depending on the charge of M, the index n takes the value zero, one, two, three or four, preferably zero, one or two. The metals mentioned above

Groups 3-7 can namely, depending on their affiliation to the subgroups, assume valences / charges of two to six, preferably two to four, of which two are compensated for by the carbanions of the metallocene compound. In the case of La ³⁺ , the index n takes on the value one and in the case of Zr ⁴⁺ the value two. with Sm ²⁺ n = zero.

For the preparation of the compounds (I), we refer to WO-A-98/45339.

Metallocene compounds of the formula (II) are also particularly suitable.

πl and πll represent differently charged or electrically neutral π systems which are mono- or di-fold with unsaturated or saturated five- or

Six rings can be condensed,

D denotes a donor atom which is a substituent of πl or part of the π system of πl and which has at least one lone pair of electrons in its respective bond state,

A denotes an acceptor atom which is a substituent of πll or part of the π system of πll and which has an electron pair gap in its respective bond state,

where D and A are linked by a reversible coordinative bond in such a way that the donor group takes on a positive (partial) charge and the acceptor group takes on a negative (partial) charge and at least one of D and A is part of the respective π system,

where D in turn can carry substituents, and A carries at least one fluorine-substituted aryl group, but preferably only fluorine-substituted aryl groups, as substituents, wherein each π system or each fused ring system can contain one or more D or A or D and A and

where in πl and πll in the uncondensed or in the condensed form, independently of one another, one to all H atoms of the π system by identical or different radicals from the group of linear or branched C ₁ -C ₂₀ alkyl, the 1-fold until completely substituted by halogen, 1-3 times by phenyl and 1-3 times by vinyl, C ₆ -C ₁₂ aryl _! , Haloaryl with 6 to 12 carbon atoms and can be substituted once or twice by D and A, so that the reversible coordinative D → A bond (i) between D and A, the two parts of the respective π-

System or of the fused-on ring system, or (ii) of which D or A is part of the π system or of the fused-on ring system and the respective other substituent of the uncondensed π system or of the fused-on ring system, or (iii) both D and A are such substituents, in the case of (iii) at least one additional D or A or both parts of the π system or the fused-on ring system is (are) formed,

M represents a metal from groups 3-7 of the Periodic Table of the Elements according to IUPAC (1985) including the lanthanides and actinides,

X represents an anion equivalent and

n depending on the charges of M as well as those of πl and πl I the number

Means zero, one, two, three or four.

Π systems according to the invention are substituted and unsubstituted ethylene, allyl, pentadienyl, benzyl, butadiene, benzene, the cyclopentadienyl anion and the species resulting from replacement of at least one C atom by a heteroatom. Among the species mentioned, the cyclic ones are preferred. The type of coordination of such ligands (π systems) to the metal can be of the σ type or of the π type. Sandwich structures in which the two π systems are selected from cyclopentadienyl (cp), indenyl (ind) and fluorenyl (flu) are particularly preferred, in particular:

cp-cp cp-ind cp-flu ind-ind ind-flu flu-fiu

Depending on the charge of M, the index n takes the value zero, one, two, three or four, preferably zero, one or two. The above-mentioned subgroup metals can namely, depending on their affiliation with the

Assume subgroups, valences / charges of two to six, preferably two to four, of which two are compensated for by the carbanions of the metallocene compound. Accordingly, in the case of La the index n takes the value one and in the case of Zr ⁴⁺ the value two; with Sm ²⁺ n = zero.

In the formation of the metallocene structure according to formula (I) or (II) above, a positive charge of the transition metal M is compensated for by a cyclopentadienyl-containing carbanion. Any remaining positive charges on the central atom M are saturated by further, mostly monovalent anions X, of which two identical or different anions can also be linked to one another (dianions xx), for example monovalent or divalent negative residues from the same or different, linear or branched, saturated or unsaturated hydrocarbons, amines, phosphines, thio alcohols, alcohols or phenols. Simple anions such as CR ₃ ^" , NR ₂ ^" , PR ₂ ^" , OR ^" , SR ^" etc. can be connected by saturated or unsaturated hydrocarbon or silane bridges, whereby dianions are formed and the number of bridge atoms 0, 1, 2, 3, 4, 5, 6 may be preferred are 0 to 4 bridge atoms, particularly preferably 1 or 2 bridge atoms. In addition to H atoms, the bridge atoms can also carry further KW substituents R. Examples of bridges between the simple anions are about -CH ₂ -, -CH ₂ -CH ₂ -, - (CH ₂ ) ₃ -, CH = CH, - (CH = CH) ₂ -, -CH = CH-CH ₂ -, CH ₂ -CH = CH-CH ₂ -, -Si (CH ₃ ) ₂ -, C (CH ₃ ) ₂ -. Examples of X are: hydride, chloride, methyl, ethyl, phenyl, fluoride,

Bromide, iodide, the n-propyl radical, the i-propyl radical, the n-butyl radical, the amyl radical, the i-amyl radical, the hexyl radical, the i-butyl radical, the heptyl radical, the octyl radical, the nonyl radical, the decyl radical, the cetyl radical, Methoxy, ethoxy, propoxy, butoxy, phenoxy, dimethylamine, diethylamino, methylethylamino, di-t-butylamino, diphenylamino, diphenylphosphino, dicyclohexylphosphino, dimethylphosphino, methylidene, ethylidene,

Propylidene, the ethylene glycol dianion. Examples of dianions are 1,4-diphenyl-1,3-butadienediyl, 3-methyl-l, 3-pentadienediyl, l, 4-dibenzyl-l, 3-butadienediyl, 2,4-hexadienediyl, 1,3- Pentadienediyl, 1,4-ditolyl-1,3-butadienediyl, 1,4-bis (trimethylsilyl) -1,3-butadienediyl, 1,3-butadienediyl. 1,4-Diphenyl-1,3-butadienediyl, 1,3-pentadienediyl, 1,4-dibenzyl-1,3-butadienediyl, 2,4-hexadienediyl, 3- are particularly preferred.

Methyl-l, 3-pentadienediyl, 1,4-ditolyl-1,3-butadienediyl and 1,4-bis (trimethylsilyl) -1,3-butadienediyl. Other examples of dianions are those with heteroatoms, such as the

Structure ₂ C Γ O _ R ₂ C Γ S _ R ₂ C ^~ NR or R ₂ C ^p R where the

Bridge has the meaning given. In addition, weak or non-coordinating anions of the abovementioned are particularly preferred for charge compensation

Kind or simply negatively charged anions of the type Cpl, cpll, πl or πll with the substitution possibilities described there, which can but do not have to carry additional D or A substituents.

The compounds of the general formula (III) can be prepared in accordance with WO-A-98/45339.

In addition to the obligatory first donor-acceptor bond between D and

A in formulas (I) and (II) further donor-acceptor bonds can be formed if additional D and / or A as substituents of the respective cyclo- pentadiene systems are available. All donor-acceptor bonds are characterized by their reversibility shown above. In the case of several D or A, they can assume different positions. The invention accordingly encompasses both the bridged molecular states and the unbridged states. The number of D groups can be the same or different from the number of A-

Be groups. The ligands, in particular Cpl and Cpll, are preferably linked via only one donor-acceptor bridge.

In addition to the D / A bridges according to the invention, covalent bridges can also be present in the formulas (I) and (II). In this case, the D / A bridges reinforce the

Stereorigidity and the thermal stability of the catalyst. When switching between closed and open D / A binding, sequence polymers with higher and lower stereoregularity become accessible. Such sequences can have different chemical compositions in copolymers.

Suitable donor groups in formulas (I) and (II) are, in particular, those in which the donor atom D is an element from groups 15, 16 or 17 of the periodic table of the elements and has at least one lone pair of electrons and where the donor atom is in the Case of elements of the 15th group is in a bonded state with substituents and can be in the case of elements of the 16th group; Donor atoms of the 17th group have no substituents. This is illustrated using the example of phosphorus P, oxygen O and chlorine CI as donor atoms as follows, where "Subst." such mentioned substituents and "-Cp" represent the bond to the cyclopentadienyl-containing carbanion, a dash with an arrow which has the meaning of a coordinative bond indicated in formula (I) or (II) and other dashes mean existing electron pairs:

- Cp The acceptor groups in formulas 0) and S) are, in particular, those whose acceptor atom A is an element from the 13th group of the Periodic Table of the Elements (according to IUPAC 1985), such as boron, aluminum, gallium, indium and thallium, is in a bonded state with substituents and has an electron gap.

D and A are linked by a coordinative bond, which is also referred to as a dative bond, where D assumes a positive (partial) charge and A a negative (partial) charge.

A distinction is accordingly made between the donor atom D and the donor group or between the acceptor atom A and the acceptor group. The coordinative bond D -> A is established between the donor atom D and the acceptor atom A. The donor group means the unit consisting of the donor atom D, the substituents which may be present and the electron pairs present; accordingly, the acceptor group means the unit consisting of the acceptor atom A, the substituents and the electron gap present.

Donor groups are those in which the lone pair of electrons is located at N, P, As, Sb, Bi, O, S, Se, Te, F, CI, Br, I; N, P, O, S are preferred thereof

Donor groups may be mentioned: (CH ₃ ) ₂ N-, (C ₂ H ₅ ) ₂ N-, (C ₃ H ₇ ) ₂ N-, (C + ft ^ N-, (C ₆ H ₅ ) ₂ N-, (CH ₃ ) ₂ P-, (C ₂ H ₅ ) ₂ P-, (C ₃ H ₇ ) ₂ P-, (iC ₃ H ₇ ) ₂ P-, (G, H ₉ ) ₂ P-, (tC H ₉ ) ₂ P-, (cyclohexyl) ₂ P-, (C ₆ H ₅ ) ₂ P-, (CH ₃ ) (C ₆ H ₅ ) P-, (CH ₃ O) ₂ P-, (C ₂ H ₅ O) ₂ P-, (C ₆ H ₅ O) ₂ P-, (CH ₃ -C ₆ H ₄ O) ₂ P-, ((CH ₃ ) ₂ N) ₂ P-, methyl-containing phosphino groups, CH ₃ O-, CH ₃ S-, C ₆ H ₅ S-, -C (C ₆ H ₅ ) = O, -C (CH ₃ ) = O, -OSi (CH ₃ ) ₃ , -OSi (CH ₃ ) ₂ -t-butyl, in which N and P each carry a free electron pair and O and S each carry two free electron pairs and where in the last two examples the double-bonded oxygen is bonded via a spacer group, and systems such as the pyrrolidone ring, the ring members other than N also act as spacers. Acceptor groups are those in which there is an electron pair gap at B, Al, Ga, In or TI, preferably B, Al or Ga; Examples include: (C ₆ F ₅ ) ₂ B-, (C ₆ F ₅ ) (alkyl) B-, (C ₆ F ₅ ) HB-, (C ₆ F ₅ ) (C ₆ H ₅ ) B-, (CH ₃ ) (C ₆ F ₅ ) B-, (VinylXC ^ B-, (Benzyl) (C ₆ F ₅ ) B-, C1 (C ₆ F ₅ ) B-, (CH ₃ O) (C ₆ F ₅ ) B-, C1 (C ₆ F ₅ ) A1-, (alkyl) (C ₆ F ₅ ) Al-, (C ₆ H ₅ ) (C ₆ F ₅ ) A1-, (C ₆ F ₅ ) ₂ A1 -, (C ₆ F ₅ ) ₂ Ga, (C ₆ F ₅ ) (alkyl) Ga.

Substituents on the donor atoms N, P, As, Sb, Bi, O, S, Se and Te and on the acceptor atoms B, AI, Ga, In and TI are, for example: -C 1 -C ₂ (cyclo) alkyl, such as methyl , Ethyl, propyl, i-propyl, cyclopropyl, butyl, i-butyl, tert-butyl, cyclobutyl, pentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, the isomeric heptyls, octyls,

Nonyle, decyle, undecyle, dodecyle; the corresponding C 1 -C ₁₂ alkoxy groups; Vinyl, butenyl, allyl; C ₆ -C ₁₂ aryl such as phenyl, naphthyl or biphenylyl, benzyl, by halogen, 1 or 2 Cι-C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, sulfonate, nitro or haloalkyl, Cι-C ₆ - Alkyl carboxy, -CC ₆ alkyl carbonyl or cyano can be substituted (for example perfluorophenyl, m, m'-bis (trifluoromethyl) phenyl, tri (C ₁ -C ₂₀ alkyl) silyl, tri (C ₆ -C ₁₂ aryl) silyl and analogous substituents familiar to the person skilled in the art); analog aryloxy groups; indenyl; Halogen such as F, Cl, Br and I, 1-thienyl, disubstituted amino, such as _(Cι-C12 alkyl) ₂ amino, diphenylamino, tris (C ₁ -C ₁₂ alkyl) silyl, aryl NaSO ₃ such as NaSO ₃ phenyl and NaSO tolyl, C ₆ H ₅ -C = C-; aliphatic and aromatic C ₁ -C ₂₀ -silyl, the alkyl substituents of which may be octyl, decyl, dodecyl, stearyl or eicosyl in addition to the abovementioned, and the aryl substituents of which may be phenyl, tolyl, xylyl, naphthyl or biphenylyl; and those substituted silyl groups which are bonded to the donor atom or the acceptor atom via -CH ₂ -, for example (CH ₃ ) ₃ SiCH ₂ -, (CrC ₁₂ -alkyl) (phenyl) amino, (-CC ₂ -alkyl) naphthyl) amino, (-CC ₁₂ alkyrpheny) ₂ - amino, C ₆ -C ₁₂ aryloxy with the above aryl groups, -C ₈ -perfluoroalkyl, perfluorophenyl. Preferred substituents are: -C ₆ -alkyl, Cs-C _δ- cycloalkyl, phenyl, tolyl, -CC ₆ alkoxy, C ₆ -C ₁₂ aryloxy, vinyl, allyl, benzyl, perfluorophenyl, F, CI, Br , Di- (C ₁ -C ₆ -alkyl) -amino, diphenylamino, but where the acceptor atom carries at least one fluorinated aryl substituent, preferably two fluorinated aryl substituents. All of the substituents on the acceptor group are preferably fluorine-substituted aryl groups.

Fluorinated here means partially or completely fluorinated, with completely fluorinated being preferred.

The acceptor group preferably contains an element of the 13th group of the PSE according to IUPAC 1985.

Aryl is understood to mean all mononuclear or polynuclear aryl radicals known to those skilled in the art, preferably having 6 to 13 carbon atoms, such as phenyl, naphthyl, fluorenyl, indenyl, which in turn can be substituted, although they have at least one, preferably exclusively, fluorine substituent , Fluorinated phenyl groups are particularly preferred, very particularly perfluorinated ones

Phenyl groups. If it is partially fluorinated aryl groups, the other substituents, which may be the same or different, are preferably selected independently of one another from the group hydrogen, C ₁ -C ₂₀ -alkyl, such as methyl, ethyl, propyl, isopropyl, butyl or iso -Butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, eicosyl, C ₁ -C ₂ o-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, hexoxy, octyloxy, decyloxy, dodecyloxy , Hexadecyloxy, octadecyloxy, eicosyloxy, halogen, such as chlorine or bromine, C ₆ -C ₁₂ aryl, such as phenyl, -C-C ₄ alkylphenyl, such as tolyl, ethylphenyl, (i-) propylphenyl, (i- / tert .) Butylphenyl, xylyl, halophenyl, such as fluoro-, chloro-, bromophenyl, naphthyl or biphenylyl, triorganylsilyl, such as trimethylsilyl (TMS), ferrocenyl and D or A, as defined above.

Donor and acceptor groups which contain chiral centers or in which 2 substituents form a ring with the D or A atom are also suitable. At this point, we expressly refer to the applications WO-A-98/01455, WO-A-98/45339, WO-A-98/01483 to WO-A-98/01487, and EP-A-1 041 086 which at the same time, for the purposes of US patent practice, are incorporated by reference into the present application.

The invention further relates to the use of the transition metal compounds described with donor-acceptor interaction, characterized in that these transition metal compounds have a fluorine-substituted aryl group on at least one acceptor group, in a ner process for the homo- or copolymerization of one or more olefins, i-olefins, alkynes or Diolefins as

Monomers or for ring-opening polyaddition in the gas, solution, bulk, high pressure or slurry phase at -60 to + 250 ° C, preferably up to + 200 ° C and 0.5 to 5000 bar, preferably 1 to 3,000 bar and in the presence or absence of saturated or aromatic hydrocarbons or of saturated or aromatic aromatic hydrocarbons and in the presence or absence of

Hydrogen, these transition metal compounds with donor-acceptor interaction being used in an amount in the range from 10 ¹ to 10 ¹² mol of all monomers per mol of transition metal compound and also in the presence of cocatalysts, such as Lewis acids, Brönstedt acids or Pearson acids or can additionally be carried out in the presence of Lewis bases.

Such Lewis acids are, for example, boranes or alanes, such as aluminum alkyls, aluminum halides, aluminum alcoholates, bororganyls, boron halides, boric acid esters or boron or aluminum compounds which contain halide as well as alkyl or aryl or alcoholate substituents, and Mixtures of these or that

Triphenyh ethyl cation. Aluminoxanes or mixtures of aluminum-containing Lewis acids with water are particularly preferred. According to current knowledge, all acids act as ionizing agents that form a metallocenium cation that is charge-compensated by a bulky, poorly coordinating anion. The invention further relates to the reaction products of such ionizing agents with compounds of the general formula (I) or (TI) according to the invention. They can be described by the general formulas (HI) or (TV)

Anion (purple)

or

Anion (Mb)

respectively.

Anion (IVa)

or Anion (IVb)

in the

Anion for the entire bulky, poorly coordinating anion and base for a Lewis base.

The transition metal compounds of the general formula (I), (II), (DI) or (IN) according to the invention can be present in either monomeric, dimeric or oligomeric form.

Examples of such poorly coordinating anions are e.g.

B (C ₆ H ₅ ) ₄ Θ, B (C ₆ F ₅ ) ₄ Θ, B (CH ₃ ) (C ₆ F5) ₃ Θ

or sulfonates such as tosylate or triflate, tetrafluoroborates, hexafluorophosphates or

-antimonates, perchlorates, and voluminous cluster molecular anions of the carborane type, for example CB ₉ H. ₂ ^Θ or CBuHπ, and substituted or unsubstituted cyclopentadienyl, indenyl and fluorenyl anions. Possible substituents are those which have also been described for Cpl and Cpll. If such anions are present, π-complex compounds can act as highly effective polymerization catalysts even in the absence of aluminoxane. This is especially the case when an X ligand represents an alkyl group or benzyl. It However, it can also be advantageous to use π complexes with voluminous anions in combination with aluminum alkylene, such as (CH ₃ ) ₃ A1, (C ₂ H ₅ ) ₃ A1, (n- / i-propyl) 3 AI, (n- / t-Butyl) ₃ Al, (i-butyl) ₃ Al, the isomeric pentyl, hexyl or octyl aluminum alkyls, or lithium alkyls, such as methyl-Li, benzyl-Li, butyl-Li or the corresponding Mg-organic compounds , such as Grignard compounds or Zn organyls. Such metal alkyls transfer alkyl groups to the central metal, on the one hand, and on the other hand, they trap water or catalyst poisons from the reaction medium or monomer in polymerization reactions. Examples of aluminum or boron compounds from which such anions can be derived are:

Triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (t-butyl) ammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate,

N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylarnmonium tetrakis (pentafluorophenyl) borate, tripropylammonium pentafluorophenyl (tetrakis)

Tri (n-butyl) ammomum tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium) tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,5-trimethylanilinium) tetrakis (pentafluorophenyl) borate,

Trimethylamminium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylarnmonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,

N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-Diemylamlmium-tefrakis (2,3,4,6-tetrafluorophenyl) borate,

N, N-dime & yl- (2,4,6-trmιemylamlinium) -tefrakis- (2,3,4,6-tetrafl

Dialkylammonium salts such as:

Di (i-propyl) ammonium tetrakis (pentafluorophenyl) borate and

Dicyclohexylammonium tetrakis (pentafluorophenyl) borate;

Tri-substituted phosphonium salts, such as:

Triphenylphosphonium tetrakis (pentafluorophenyl) borate,

Tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate,

Tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate,

Tritolylmethyl tetrakis (pentafluorophenyl) borate,

Triphenylmethyl-tetraphenylborate (trityl-tetraρhenylborate),

Trityl tetrakis (pentrafluo henyl) borate,

Silver tetrafluoroborate,

Tris (pentafluorophenyl) borane,

Tris (trifluoromethyl) borane and the analog aluminum compounds.

The transition metal compounds or metallocene compounds according to the invention can be used in isolation as pure substances for (co) polymerization. However, it is also possible to generate and use them "in situ" in the (co) polymerization reactor in a manner known to the person skilled in the art.

Other cocatalysts are, for example, aluminoxane compounds. These include those of the formula (V)

understood in the

R represents C ₁ -C ₂ o-alkyl, C ₆ -C ₂ aryl or benzyl and n is a number from 2 to 50, preferably 10 to 35.

It is also possible to use a mixture of different aluminoxanes or a mixture of their precursors (aluminum alkyls or alkyl aluminum halides) in combination with water (in gaseous, liquid, solid or bound form, for example as water of crystallization). The water can also be supplied as the (residual) moisture of the polymerization medium, the monomer or a carrier such as silica gel or aluminosilicate.

The bonds protruding from the square brackets of formula (V) contain R groups or A1R groups as end groups of the oligomeric aluminoxane. Such aluminoxanes are generally present as a mixture of several of them with different chain lengths. The fine examination has also revealed aluminoxanes with an annular or cage-like structure. Aluminoxanes are commercially available

Links. In the special case of R = CH ₃ , one speaks of methylaluminoxanes (MAO).

The transition metal compound / compounds and / or the cocatalyst / the cocatalysts can be used both as such in homogeneous form and individually or together in heterogeneous form on supports. The carrier material can be inorganic or organic in nature, such as silica gel, B ₂ O ₃ , Al ₂ O ₃ , MgCl ₂ , cellulose derivatives, starch and polymers or else layered silicates, such as montmorrillonite.

Carrier materials are preferably thermally and / or chemically pretreated in order to adjust the water content or the OH group concentration in a defined manner or to keep it as low as possible. Chemical pretreatment can consist, for example, of reacting the support with aluminum alkyl. Inorganic carriers are often heated to 100 ° C to 1000 ° C for 1 to 100 hours before use. The surface of such inorganic supports, in particular of silica (SiO ₂ ), is between 10 and 1000 m ² / g, preferably between 100 and 800 m ² / g. The particle diameter is between 0.1 and 500 micrometers (μ), preferably between 10 and 200 μ.

Olefins, i-olefins, cycloolefins, alkynes and diolefins to be reacted by homo- or copolymerization are, for example, ethylene, propylene, butene-1, i-butene, pentene-

1, hexene-1, octene-1, 3-methyl-butene-1, 4-methyl-pentene-1, 4-methyl-hexene-1, 1,3-butadiene, isoprene, 1,4-hexadiene, 1 , 5-hexadiene and 1,6-octadiene or methyl octa- dienes, chloroprene, acetylene, methylacetylene. With α, ω-diolefins, a cyclizing polymerization can furthermore be carried out, in which poly- (methylene-1,3-cyclopentane) is formed, for example, from 1,5-hexadiene:

α, ω-diolefms can also be used to generate long chain branches.

If trialkylsilyl-substituted α, ω-diolefms are used, a functional group can subsequently be introduced by polymer-analogous reaction.

The olefins and diolefins can also be substituted, for example with

Phenyl, substituted phenyl, halogen, the esterified carboxyl group, the acid anhydride group; Compounds of this type are, for example, styrene, methylstyrene, chlorostyrene, fluorostyrene, indene, 4-vinyl-biphenyl, vinyl-fluorene, vinyl-anthracene, methyl methacrylate, ethyl acrylate, vinylsilane, trimethylallylsilane, vinyl chloride, vinylidene chloride, tetrafluoroethylene, isobutylene, vinylcarbrolidone, vinylpyrrolidone Acrylonitrile

Vinyl ethers and vinyl esters or vinyl norbornene.

Furthermore, ring-opening polyadditions according to the invention, for example of lactones, such as ε-caprolactone or δ-valerolactone, of lactams, such as ε-caprolactam or of Epoxides such as ethylene oxide or propytenoxide or from other cyclic ethers such as tetrahydrofuran possible.

Cycloolefins which can be used are described in the applications WO-98/01483 and WO-98/01484.

Preferred monomers are: ethylene, propylene, butene, hexene, octene, 1,5-hexadiene, 1,6-octadiene, cycloolefins, methyl methacrylate, ε-caprolactone, δ-valerolactone and acetylene. It is possible to carry out the (co) polymerizations mentioned in the presence of hydrogen, for example to adjust the molecular weight.

The homo- or copolymerizations or polyadditions to be carried out with the optionally supported transition metal compounds with a donor-acceptor interaction are carried out adiabatically or isothermally in the range of the temperatures and pressures indicated. These are high-pressure processes in autoclaves or tubular reactors, solution processes and bulk polymerization, processes in the slurry phase in stirred reactors or loop reactors and processes in the gas phase, the pressures for the slurry, solution and and gas phase do not exceed 100 bar. Such polymerizations can also be carried out in the presence of hydrogen. All of these methods have been known for a long time and are familiar to the person skilled in the art.

The optionally supported, transition metal compounds according to the invention with a donor-acceptor interaction enable a defined opening of the two cyclopentadienyl skeletons or the two through the donor-acceptor bridge

Ligands in the manner of a beak, where, in addition to high activity, high stereoselectivity, controlled molecular weight distribution and uniform incorporation of comonomers are possible. As a result of a defined beak-like opening, there is also space for voluminous comonomers. A high uniformity in the molecular weight distribution results from the uniform and Defined location of the polymerization (insertion) (single site catalyst).

The D / A structure can bring about an extra stabilization of the catalysts up to high temperatures, so that the catalysts also in the high temperature range of

80 to 250 ° C, preferably 80 to 180 ° C can be used. The possible thermal dissociation of the donor-acceptor bond is reversible and leads to particularly high-quality catalyst properties due to this self-assembly process and self-repair mechanism. Thermal dissociation enables e.g. a targeted broadening of the molecular weight distribution, which makes the polymers easier to process. This effect comes e.g. also applicable to those catalysts in which the ligands, e.g. Cpl and Cpll, each linked by a covalent and a D / A bridge. The D / A metallocene structures according to the invention enable e.g. a level of defect-free polyethylene formation not achieved with classic catalysts. Accordingly, the ethene polymers can have extraordinarily high melting temperatures, for example above 135 ° C. to 160 ° C. (maximum of the DSC curve). Such high-melting polyethylenes, given the known, for example, improved mechanical properties and heat resistance (sterilizability in medical applications) and thereby open up application possibilities which previously were not possible for polyethylene and, for example, were previously only achievable with highly tactical polypropylene. Other features include high melting enthalpies and high PE mastic masses. In particular, the catalysts according to the invention enable the polyethylene chains to grow to extremely high molecular weights without problems.

In a wide temperature range, the PE molar mass is reduced by increasing the polymerization temperature, but without any appreciable reduction in activity and without leaving the area of technically interesting high PE molar masses and high PE melting temperatures. It was also observed that transition metal compounds according to the invention with a donor-acceptor interaction of suitable symmetry on suitable monomers bring about a regiospecific (isotactic, syndiotactic) polymerization, but trigger an increasingly unspecific (atactic) linkage of the monomer units on the same monomer in the upper part of the temperature range mentioned. This phenomenon has not yet been fully investigated, but could be in agreement with the observation that coordinative bonds which are overlaid by an ionic bond, such as the donor-acceptor bonds in the metallocene compounds according to the invention, show increasing reversibility at higher temperatures , In ethylene-propylene copolymerization, for example, it was observed that with the same supply of both comonomers, a copolymer containing high propylene is formed at a low polymerization temperature, while the propylene content decreases with increasing polymerization temperature, until finally at high temperature, predominantly ethylene-containing polymers are formed ,

The reversible dissociation and association of the D / A structure and the consequent rotation of the ligands, for example of the Cp frameworks, can be represented schematically as follows:

D / A bridged

Another valuable property of the supported catalysts according to the invention with a donor-acceptor interaction is the possibility of self-activation and thus the elimination of expensive cocatalysts. In this case, the acceptor atom A binds one in the opened form of the D / A metallocene compound. X ligands form a zwitterionic structure and thus generate a positive charge on the transition metal, while the acceptor atom A generates a negative one Takes charge. Such self-activation can take place intramolecularly or intermolecularly. This is illustrated by the example of linking two X ligands to form a chelate ligand, namely the butadiene diyl derivative:

activated form

The binding site between the transition metal M and H or substituted or unsubstituted C, for example the still bonded C of the butadiene diyl dianion shown in the formula example, is then the place for the olefin insertion for the polymerization.

Furthermore, the optionally supported, transition metal compounds with a donor-acceptor interaction are suitable for the production of both thermoplastic and elastomeric polymers by the various production processes mentioned above, both highly crystalline polymers with an optimized melting range and amorphous polymers with an optimized glass transition temperature being accessible. Of particular interest are the polymers that can be produced in this way with a low glass transition temperature below 0 ° C and a high melting temperature> 100 ° C in the same material.

The polymers that can be produced are particularly suitable for the production of all types of molded articles, in particular foils, tubes also for medical purposes, profiles, disks, optical data storage media, cable sheathing and extrudates, for surgical implants, ski tread materials, impact modifiers for thermoplastics, for example for Bumpers on the car etc.

The following examples illustrate the invention. Examples

All reactions were carried out under strictly anaerobic conditions and using Schlenk techniques or the high vacuum technique. The solvents used were dry (pentane, hexane, heptane, with L1AIH4; toluene with

Sodium, diethyl ether with sodium / benzophenone; Methylene chloride with CaH2) and saturated with argon. Chemical shifts δ are given in ppm, relative to the respective standard: ^ (tetramethylsilane), ¹³ C (tetramethylsilane), ¹⁹ F (CC1 ₃ F), ³ Negative signs mean a shift to a higher field.

example 1

Dimethylbis (pentafiuorphenyl) tin, (CH ₃ ) ₂ Sn (C ₆ Fs) ₂ (compound 1)

A two-necked round-bottom flask equipped with Mg chips (4.54 g, 187 mmol) and a stirrer equipped with a cooler and dropping funnel with pressure equalization was thoroughly dried under vacuum and heating. Then 200 ml of freshly distilled sodium-dried diethyl ether and an iodine crystal were introduced into the flask via a cannula. Bromopentafluorobenzene (dried over CaH ₂ and freshly distilled, 46.12 g, 187 mmol) was introduced into the dropping funnel via a cannula and then added to the Mg suspension so slowly that the batch remained under gentle reflux during the addition. The mixture was refluxed for four hours and cooled to 0 ° C. A solution of dimethyltin dichloride, Me ₂ SnCl ₂ , (20.5 g, 93 mmol) in 150 ml of freshly distilled diethyl ether was then added via a cannula within 30 minutes. The mixture was warmed to room temperature and stirred under argon overnight. After replacing the cooler with a short path distillation apparatus and distilling off most of the diethyl ether, 200 ml of freshly distilled toluene were added. The distillation was continued until the diethyl ether was completely removed from the batch. The toluene solution was filtered at room temperature under argon and the solid washed with toluene (10 ml X 3). The toluene was removed from the combined filtrates under reduced pressure. The product was under vacuum

(3 x 10 ^" mbar, 110-140 ° C) distilled, whereby the primary flask was cooled

Final product was obtained as a colorless solid which was dense at room temperature

(41.0 g, 90% yield).

1H NMR (400.13 MHz, CD ₂ C1 ₂ ); δ 0.83 (s, with ¹¹⁷ Sn / ¹¹⁹ Sn satellites).

¹⁹ F NMR (376.3 MHz, CD ₂ C1 ₂ ); δ -122.0 (m, 4F, ortho), -151.7 (m, 2F, para), -160.7

(m, 4F, meta).

1). R. D. Chambers and T. Chivers. J. Chem. Soc. 1965, 3933. 2). D. J. Parks, R. E. H. Spence and W. E. Piers. Angew. Chem. 1995, 107, 895. 3). R. E. H. Spence, D. J. Parks, W. E. Piers, M.-A. MacDonald, M. J. Zawarotko and S. J. Rettig. Angew. Chem. 1995, 107, 1337.

Example 2

Bis (pentafluorophenyl) boron chloride, (C ₆ F ₅ ) ₂ BC1 (compound 2)

A solution of dimethylbis (pentafluorophenyl) tin, Me ₂ Sn (C ₆ F ₅ ) was placed in a thoroughly dried 500 ml Schlenk tube with a side arm with J-Young cock, Teflon / rubber double O-ring stopper and stirrer core. ₂ , (40.98 g, 84.9 mmol) in 30 ml of dry heptane. The solution was cooled to -70 ° C. and a solution of BC1 ₃ (85 ml of a 1.0 M solution in heptane, 85 mmol) was added via a syringe. The Schlenk tube was sealed and the solution was allowed to warm slowly to room temperature and stirred at RT for 2.5 hours. Some precipitation occurred. The Schlenk tube was then heated with a 105 ° C oil bath for 30 hours. Some crystals can condense in the upper part of the tube. The mixture was allowed to cool slowly to room temperature overnight, a large amount of Me ₂ SnCl ₂ crystals precipitating out of the solution. The supernatant was cannulated into another thoroughly dried flask, after which the crystals were washed with hexane (20 ml X 2), which was combined with the supernatant. By drying the crystals, pure Me ₂ SnCl _{2 was} recovered to more than 90%. After the volatile constituents had been stripped off from the solution under reduced pressure, the off-white solid was briefly dried under vacuum, giving 31.3 g of crude product, which was redissolved in the smallest possible amounts of hexane. After filtering off the insoluble components (mainly Me ₂ SnCl), the clear solution was cooled to -30 ° C. overnight. The supernatant was cannulated off while the solution was still cold, and the crystals were dried under vacuum, giving the pure compound C1B (C ₆ F ₅ ) ₂ ,

(26.42 g, 82%) in the form of extremely air and moisture sensitive crystals.

^U B-MR (80.25 MHz, CD ₂ C1 ₂ ); δ 58.0 (br. s) ¹⁹ F NMR (376.3 MHz, CD ₂ C1 ₂ ); δ -129.5 (m, 4F, ortho), -145.5 (m, 2F, para), -161.6 (m, 4F, meta).

l. a). R. Duchateau, S.J. Lancaster, M. Thornton-Pett and M. Bochmann. Organometallics 1997, 16, 4995. b). M. Bochmann, S.J. Lancaster and O. B. Robinson. J. Chem. Soc. Chem. Commun. 1995, 2081.

2. a). R. D. Chambers and T. Chivers. J. Chem. Soc. 1965, 3933. b). D. J. Parks, R.

E. H. Spence and W. E. Piers. Angew. Chem. 1995, 107, 895. c). R. E. H. Spence, D. J. Parks, W. E. Piers, M.-A. MacDonald, M. J. Zawarotko and S. j. Rettig. Angew. Chem. 1995, 107, 1337.

3. SJ Lancaster, M. Thornton-Pett, DM Dowson and M. Bochmann. Organometallics 1998, 77, 3829. Example 3

l-trimethylstannyl-2-methylindene, (CH ₃ ) ₃ Sn (C ₉ H ₆ ) CH ₃ (compound 3)

A solution of 2-methylindene (14.62 g, 112.3 mmol) in 400 ml of hexane was injected at -70 ° C. using a syringe with BuLi (48 ml of a 2.5 molar solution in hexane, 120.0 mmol) The mixture was stirred under argon and allowed to warm slowly to room temperature overnight. After the volatiles had been separated off by filtration through a cannula, the white solid became

Removal of excess BuLi washed with hexane (50 ml x 3). The solid was then suspended in 300 ml of hexane and a solution of chlorotrimethyltin, Me ₃ SnCl (22.40 g, 112.4 mmol) in 100 ml of hexane was added via cannula at 0 ° C. The resulting mixture was heated under reflux for 2.5 hours and stirred at room temperature for 16 hours. The white precipitate was filtered off and the filtrate was freed from volatiles under reduced pressure. The oily residue was distilled under reduced pressure to give 31.35 g of a yellow oil (95% crude yield). According to 1H-NMR, the product is spectroscopically pure.

NMR:

1H: (400.13MHz, C ₆ D ₆ ): δ 7.44 (d, J = 7.5Hz, 1H), 7.28 (d, J = 7.5Hz, 1H), 7.21 (t, J = 6.7Hz, 1H), 7.13 (t, J = 6.6Hz, 1H), 6.49 (s, 1H), 3.55 (s, 1H), 1.99 (s, 3H), -0.11 (s, 9H).

¹³ C: (100.6MHz, C ₆ D ₆ ): δ 146.7, 145.7, 143.6, 124.3, 122.6, 122.4, 121.4, 120.3, 47.6, 16.7., -9.8. Example 4

Bis (trimethylstannyl) -2-methylinden, {(CH ₃ ) ₃ Sn} ₂ (C ₉ H ₅ ) CH ₃ (compound 4)

l-Trimethylstannyl-2-methylinden (CH ₃ ) ₃ Sn (C ₉ H ₆ ) CH ₃ (17.0 g, 58.0 mmol) was injected at room temperature using a syringe with dimethylaminotrimethyltin, Me ₃ SnNMe ₂ , (13, 9 g, 66.9 mmol) were added, after which the mixture was heated with an oil bath at 105-110 ° C. for 12 h and stirred for a further 16 h at room temperature. After removal of volatile constituents in vacuo, the short path distillation of the oily residue gave 26.37 g (99.7% yield) a pale yellow oil which slowly solidified at room temperature. According to 1H-NMR, the product is a spectroscopically pure title compound.

NMR:

1H: (400.13MHz, C ₆ D ₆ ); δ 7.55 (d, J = 7.4Hz, 1H), 7.43 (d, J = 7.4Hz, 1H), 7.21 (t, J = 7.4, 1H), 7.15 (t, J = 7.6, 1H), 6.70 (see , 1H), 2.12 (s, 3H), 0.0 (s, 9H).

¹³ C: (100.6MHz, C ₆ D ₆ ); δ 149.6, 149.1, 143.4, 123.3, 122.3, 122.1, 121.4, 120.3,

17.7, -8.5.

Example 5

2-methyl-4-phenylindenyl lithium,

Li [2-CH ₃ -4-C ₆ H ₅ - (C ₉ H ₅ )] (compound 5)

A solution of 2-methyl-4-phenyl-indene [1] (33.58 g, 0.163 mol) in 350 ml of dry hexane was sprayed with BuLi (65.2 ml a 2.5 molar solution in hexane, 0.163 mol). The mixture was slowly warmed to room temperature overnight under an Ar atmosphere calmly. The pale yellow suspension was filtered and the solid was washed with hexane (2 x 60 ml) and dried to constant weight under high vacuum. The product was obtained in the form of a pale yellow, loose powder (31.04 g, 90%).

1H-NMR (400.13 MHz, THF-d ₈ ), δ 7.80 (dd, Jι = 8.2Hz, J ₂ = 1.4Hz, 2H), 7.28 (t,

J = 7.6Hz, 2H), 7.16 (d, J = 7.5Hz, 1H), 7.10 (t, J = 7.3Hz, 1H), 6.49 (m, 2H), 6.01 (s, 1H), 5.81 (s, 1H), 2.36 (s, 3H).

[1]. W. Spaleck, F. Küber, A. Winter, J. Rohrmann, B. Bachmann, M. Antberg, V. Dolle and E. F. Paulus. Organometallics, 1994, 13, 954.

Example 6

Bis (trimethylstannyl) -2-methyl-4-phenylinden, {(CH ₃ ) ₃ Sn} ₂ -2-CH ₃ -4-C ₆ H ₅ - (C ₉ H ₅ ) (Compound 6)

A suspension of 2-methyl-4-phenyl-indenyllithium, Li [2-Me-4-Ph- (C ₉ H ₅ )], (18.98 g, 89.4 mmol) in 200 ml of dry hexane was - A solution of chlorotrimethyltin, ClSnMe ₃ (17.82 g, 89.4 mmol) in 60 ml of dry hexane was added at 70 ° C. over a cannula within 15 minutes. The mixture was allowed to warm slowly to room temperature overnight. The white suspension was filtered through Celite to remove LiCl and the volatiles were removed from the filtrate under reduced pressure. The remaining oil was kept under vacuum for 15 minutes, leaving 32.34 g (98%) of a viscous oil which was pure by 1H-NMR. The product was dissolved in an equivalent amount of trimethyltin dimethylamide, Me ₂ N-SnMe ₃ , (18.22 g, 87.6 mmol). After heating the mixture with a hot oil bath at 110 ° C. for 20 hours, the highly viscous liquid was freed from small volatile components in vacuo. The residue slowly solidified at room temperature to 45.07 g (96.7%) of an olive-green solid which was pure by 1H NMR spectroscopy. 1H NMR (400.13 MHz, CD ₂ C1 ₂ ), δ 7.64 (m, 2H), 7.49 (t, J = 7.4Hz, 2H), 7.27 (m, 2H), 7.18 (m, 2H), 6.88 (s, 1H), 2.28 (s, 3H), 0.13 (s, 18H).

Example 7

Fluorenyllithium, Li (C ₁₃ H ₉ ) (Compound 7)

A solution of fluorene (11.09 g, 66.74 mmol) in 300 ml of dry pentane was mixed with BuLi (28.0 ml of a 2.5 molar solution, 70.0 mmol) at -70 ° C. The pale yellow solution obtained was stirred under an Ar atmosphere for 16 hours at room temperature and then heated under reflux for 24 hours. The orange-yellow solution was filtered through a cannula and the yellow solid residue was washed with pentane (2 × 100 ml, each about 15 minutes under reflux) and filtered. The orange-yellow powder was dried to constant weight under dynamic vacuum to give 9.10 g (79.2%) of loose orange powder as a pure fluorenyllithium product.

^ -NIMR: (400.13 MHz, THF-d ₈ ), δ 7.86 (d, J = 7.53Hz, 2H), 7.25 (d, J = 7.96Hz, 2H), 6.75 (td, J _! = 6.65Hz. J ₂ = 1.22Hz, 2H), 6.37 (t, J = 7.64Hz, 2H), 5.88 (s, 1H).

1) J.B. Grutzner et al. J. Amer. Chem. Soc (1972), 94, 2306

2) J. J. Brooks et al. J. Amer. Chem. Soc (1972), 94, 7339

3) R. Zerger et al. J. Amer. Chem. Soc (1974), 96, 5441 Example 8

Trimethylsilyldimethylphosphino-cyclopentadiene, (CH ₃ ) ₃ Si (C ₅ H ₄ ) P (CH ₃ ) ₂ (Compound 8)

A suspension of lithium trimethylsilylcyclopentadienide, Li (C ₅ H ₄ ) SiMe ₃ , (7.82 g, 54.2 mmol) in 100 ml hexane was cannulated with a solution of chlorodimethylphosphine at -70 ° C. within 15 min. ClPMe ₂ , (5.32 g, 54.0 mmol) in 20 ml hexane. The mixture was allowed to warm slowly to room temperature with stirring under an Ar atmosphere overnight. To

Filtration of the suspension over Celite to separate LiCl, the filtrate was freed of volatile components under reduced pressure. The crude product obtained was 10.2 g (95%) of an oily yellow residue which is pure by 1 H and 31 P NMR spectroscopy. A short yellow distillation of the crude product gave a light yellow oil (9.33 g, 87%). 1H and ³¹ P NMR spectra show a complicated mixture of isomers.

Example 9

Trimethylsilyl diethylphosphino-cyclopentadiene,

(CH ₃ ) ₃ Si (C ₅ H ₄ ) P (C ₂ H ₅ ) ₂ (compound 9)

A suspension of lithium trimethylsilylcyclopentadienide, Li (C ₅ H ₄ ) SiMe ₃ , (5.8 g, 40 mmol) in 100 ml hexane was cannulated at -70 ° C within 25 min. With a solution of chlorodiethylphosphine, C1P ( CH ₂ CH ₃ ) ₂ , (4.87 g, 39.1 mmol) in

50 ml of hexane are added. The suspension obtained was stirred under an Ar atmosphere and allowed to warm slowly to room temperature overnight. After filtering the suspension through Celite, the filtrate was devolatilized to give a light yellow oil (7.53 g, 83%) which was redistilled under reduced pressure to give a pale yellow oil (6.96 g, 78.6 %) as a mixture of isomers, l-trimethylsilyl-3-diethylphosphinocyclopentadiene being the main product. Example 10

Trimethylsilyl-diisopropylphosphino-cyclopentadiene, (CH ₃ ) 3Si (C ₅ H4) P {CH (CH ₃ ) 2} 2 (Compound 10)

A solution of lithium diisopropylphosphinocyclopentadienide, Li (C ₅ H ₄ ) P (CHMe ₂ ) ₂ ,

(4.32 g, 23 mmol) in 60 ml hexane was carried out at -70 ° C within 25 min

Cannula with a solution of trimethylchlorosilane, Me ₃ SiCl, (2.5 g, 23 mmol) in

40 ml of hexane are added. The mixture was stirred under an Ar atmosphere overnight. After filtering the suspension obtained to separate LiCl, the filtrate was freed from volatile components under reduced pressure, where as

Crude product an orange oil remained (3.28 g, 56%). The crude product was distilled under vacuum (> 80 ° C / 3.5 x 10 ^" mbar), which is a light yellow oil

(2.01 g) as a position isomer mixture.

Example 11

Trimethylsilyl-diphenylphosphino-cyclopentadiene, (CH ₃ ) ₃ Si (C ₅ H4) P (C ₆ H ₅ ) 2 (Compound 11)

A suspension of lithium trimethylsilylcyclopentadienide, Li (C ₅ H) SiMe ₃ , (5.79 g, 40.15 mmol) in 100 ml of hexane was cannulated with a solution of chlorodiphenylphosphine, C1P at -70 ° C. within 15 min (C ₆ H ₅ ) ₂ , (8.8 g, 40.15 mmol) in 50 ml of hexane. The mixture was allowed to warm slowly to room temperature overnight. The orange suspension was over a

Frit # 3 filtered and the solid washed with CH ₂ C1 ₂ (30 ml x 2). After the volatile components had been stripped off from the filtrate under reduced pressure, a dark brown, thick oily residue remained which was distilled under high vacuum (200 ° C./3.3 × 10 ^-3 mbar), giving a yellow viscous liquid (11.62 g, 90 The distilled product was kept under vacuum for 2 hours at room temperature to remove residual traces of chlorodiphenylphosphine, and H and ³¹ P NMR spectra show a complicated mixture of isomers. Example 12

Dimethylphosphino-2-methyl-4-phenylindenyllithium, Li [(CH ₃ ) 2P-2-CH ₃ -4- (C ₆ H ₅ ) - (C ₉ H ₄ )] (Compound 12)

A suspension of 2-methyl-4-phenylindenyllithium, Li [2-Me-4-Ph- (C ₉ H ₅ )], (3.22 g, 15.2 mmol) in 30 ml of dry pentane was added at -70 ° C, a solution of chlorodimethylphosphine, ClPMe ₂ , (1.464 g, 15.2 mmol) in 15 ml of dry pentane was added over a cannula within 10 min. The mixture was allowed to warm slowly to room temperature overnight. The suspension was then filtered through Celite and devolatilized under reduced pressure, leaving 3.16 g (78%) of a yellow oil which, according to 1 H and 31 P NMR spectroscopy, was dimethylphosphino 2-methyl-4-phenylinden traded. The product (3.16 g, 11.87 mmol) was diluted in 50 ml dry pentane and cooled to -70 ° C. BuLi (4.80 ml of a 2.5 molar solution in hexane, 12.0 mmol) was added to the cold solution using a syringe. The mixture was allowed to warm slowly to room temperature and stir overnight. The yellow suspension obtained was filtered through a cannula and the solid residue was washed with pentane (3 × 15 ml), giving 3.02 g (93.5%) of a loose yellow

Solid remained, which according to 1-H and 31 P NMR spectroscopy was the title compound dimethylphosphino-2-methyl-4-phenylindenyllithium.

NMR for the final product l-dimethylphosphino-2-methyl-4-phenylindenyllithium

(Major isomer).

1H (400.13 MHz, THF-d ₈ ), δ 7.73 (dd, Jι = 8.2Hz, J ₂ = 1.3Hz, 2H), 7.53 (d, J = 7.4Hz, 1H), 7.21 (t, J = 7.8Hz , 2H), 7.02 (t, J = 7.4Hz, 1H), 6.39 (m, 2H), 6.00 (d, J-3.9Hz, 1H), 2.46 (s, 3H), 1.38 (d, J = 3.6Hz , 6H).

31 P (161.9 MHz, THF-d ₈ ), δ -73.0 ppm. Example 13

Diethylphosphino-2-methyl-4-phenylindenyllithium, Li [(C ₂ H ₅ ) ₂ P-2-CH ₃ -4-C ₆ H ₅ - (C ₉ H ₄ )] (Compound 13)

A suspension of 2-methyl-4-phenylindenyllithium, Li [2-Me-4-Ph- (C ₉ Hs)], (1.672 g, 7.88 mmol) in 20 ml of dry pentane was dried at -70 ° C. over a A solution of chlorodiethylphosphine, ClPEt ₂ , (0.981 g, 7.88 mmol) in 15 ml of pentane was added to the cannula. The mixture was allowed to warm slowly to room temperature overnight. The yellow suspension was filtered through Celite and freed from volatiles under reduced pressure, leaving 2.28 g (98%) of a pale yellow oil which, according to 1 H and 31 P NMR spectroscopy, was diethyl phosphino-2-methyl-4-phenylinden traded. The product obtained above (2.28 g, 7.75 mmol) was diluted in 35 ml dry pentane and cooled to -70 ° C.

The solution was then mixed with BuLi (3.2 ml of a 2.5 molar solution in hexane, 8.0 mmol). The mixture was slowly warmed to room temperature and stirred overnight. The pale yellow suspension was filtered through a cannula and the remaining solid was washed with pentane (3 x 10 ml) and dried under vacuum. 1.90 g (81.7%) of a yellow powder were obtained, which was the title compound by 1 H and 31 P NMR spectroscopy. Main isomer: diethylphosphino-2-methyl-4-phenylindenyllithium.

NMR:

1H (400.13 MHz, THF-d ₈ ), δ 7.82 (d, J = 7.6Hz, 2H), 7.53 (d, J = 7.5Hz, 1H), 7.28 (t, J = 7.6Hz, 2H), 7.09 ( t, J = 7.2Hz, 1H), 6.45 (m, 2H), 6.12 (d, J = 3.6Hz, 1H), 2.53 (s, 3H), 2.01 (m, 2H), 1.82 (m, 2H), 1.01 (t, J = 7.6Hz, 3H), 0.97 (t, J = 7.7Hz, 3H).

31 P (161.9 MHz, THF-d ₈ ), δ -36.0 ppm (singlet). Example 14

Trimethylstannyl-2-methyl-diethylphosphino-4-phenylindene, (CH ₃ ) ₃ Sn -2-CH ₃ -3- C2H _s ) ₂ P-4-C ₆ H ₅ - (C ₉ H ₄ ) (Compound 14)

Diethylphosphino-2-methyl-4-phenylindenyl-lithium (6.62 mmol) was suspended in 30 ml of hexane and cooled to -70 ° C. and then with a solution of chlorotrimethyltin, ClSnMe ₃ , (1.32 g, 6, 62 mmol) in 15 ml of hexane. The mixture was warmed to room temperature and stirred for a further 3 hours. The suspension was then filtered through Celite and volatile components were removed under reduced pressure. The viscous oil was evacuated for a further 15 minutes. This gave 2.72 g (90%) of a yellowish brown oil, which was the title compound, Me ₃ Sn-2-Me-Et ₂ P-4-Ph- (C ₉ H ₄ ).

Example 15

9-dimethylphosphinofluorenyllithium, Li [9- (CH ₃ ) ₂ P- (Cι ₃ H ₈ )] (compound 15)

A suspension of fluorenyllithium, (C ₁₃ H ₉ ) Li, (1.788 g, 10.39 mmol) in 30 ml dry pentane was cannulated at -70 ° C within 10 min with a solution of chlorodimethylphosphine, ClPMe ₂ , (1.0 g, 10.39 mmol) in 20 ml of pentane. After briefly stirring at -70 ° C., the cooling bath was removed and the mixture was stirred under an Ar atmosphere for 4 hours at room temperature (with occasional heating with a hair dryer). The suspension was mixed with 20 ml of toluene to help dissolve the product. The pale yellow suspension was filtered and the filtrate was freed from volatiles in vacuo, leaving 2.34 g (99.6%) of a pale yellow oil as 9-dimethylphosphinofluorene which, according to 1 H and 31 P NMR, was pure is. The product 9-dimethylphosphino fluorene (2.34 g, 10.34 mmol) was diluted in 25 ml of pentane and cooled to -70 ° C. The cooled solution was washed with BuLi (4.20 ml of a 2.5 molar solution, 10.5 mmol) and briefly stirred at -70 ° C and then at room temperature. The clear yellow solution slowly becomes cloudy at room temperature and yellow precipitates begin to form. After a reaction time of 5 hours at room temperature, the mixture was filtered through a cannula and the yellow solid was washed with dry pentane (3 5 ml) and dried under high vacuum, leaving 1.91 g (80%) of an orange-yellow loose solid which was according to 1 H and 31 P NMR spectroscopy is the title compound 9-dimethylphosphinofluorenyl-lithium.

NMR:

1H (400.13 MHz, THF-d ₈ ), δ 7.81 (d, J = 7.8Hz, 2H), 7.71 (d, J = 8.2Hz, 2H), 6.80 (t, J = 7.8Hz, 2H), 6.44 ( t, J = 7.3Hz, 2H), 1.44 (d, J = 3.4Hz, 6H).

³¹ P (161.9MHz, THF-d ₈ ), δ -76.7 (singlet).

Example 16

9-Diethylphosphinofluorenyllithium, Li [9- (C2H ₅ ) 2P- (Ci3H ₈ )] (Compound 16)

A suspension of fluorenyllithium, (C ₁₃ H ₉ ) Li, (2.728 g, 15.85 mmol) in 30 ml dry pentane was washed at -70 ° C with a solution of chlorodiethylphosphine, C1PE. ₂ , (1.974 g, 15.85 mmol) in 25 ml of pentane. The mixture was stirred briefly at -70 ° C and then reacted for 6 hours at room temperature. The yellow one

The suspension was filtered and the filtrate was freed from volatiles in vacuo, leaving 3.49 g (86.6%) of an orange oil which, according to 1 H and 31 P NMR spectroscopy, was 9- Diethylphosphinofluoren acted. The compound obtained above (9-diethylphosphinofluorene, 3.388 g, 13.3 mmol) was diluted in 45 ml of dry pentane and cooled to -70.degree. BuLi (5.4 ml of a 2.5 molar solution, 13.5 mmol) was added to the cooled solution and briefly touched. The mixture was stirred for 4.5 hours at room temperature with occasional heating with a hair dryer, with some loose orange precipitates forming. The reaction mixture was filtered through a cannula and the solid was washed with pentane (2 x 5 ml) and dried under vacuum, leaving an orange solid which was 1 - H and 31 P NMR spectroscopy. Diethylphosphinofluorenyllithium traded.

NMR:

1H (400.13 MHz, THF-d ₈ ), δ 7.79 (d, J = 7.5Hz, 2H), 7.68 (d, J = 8.2Hz, 2H), 6.76

(dt, Jι = 6.8Hz, J ₂ = 1.3Hz, 2H), 6.41 (dt, J. = 6.8Hz, J ₂ = 0.8Hz, 2H), 2.08 (m, 2H), 1.82 (m, 2H), 0.90 (m, 6H).

³¹ P (161.9MHz, THF-d ₈ ), δ -40.4 (singlet).

Example 17

9-Diisopropylphosphinofluorenyllithium,

Li [9 - {(CH3) 2CH} ₂ P- (C ₁₃ H8)] (Compound 17)

A suspension of fluorenyllithium, Li (C ₁₃ H ₉ ), (1.696 g, 9.85 mmol) in 30 ml dry pentane was cannulated at -70 ° C within 15 min with a solution of chlorodiisopropylphosphine, ClP (i -Pr) ₂ , (1.503 g, 9.85 mmol) in 15 ml of dry pentane. The orange suspension was slowly allowed to warm to room temperature and stirred overnight. Then the yellow one

The suspension is filtered through Celite and the filtrate is freed from volatile components in vacuo. This gave 2.68 g (96.5%) of a viscous orange oil which, according to 1 H and 31 P NMR spectroscopy, was 9-diisopropylphosphinofluorene. The product 9-diisopropylphosphinofluorene (2.68 g, 9.49 mmol) was diluted in 50 ml dry pentane, cooled to -70 ° C and with

BuLi (4.0 ml of a 2.5 molar solution, 10.0 mmol) was added. The mixture was Allow to warm up slowly to room temperature under an Ar atmosphere overnight. The orange suspension was filtered through a cannula and the solid washed with dry pentane (2 x 15 ml) and dried under high vacuum to give 2.58 g (94%) of an orange powder which was 1-H- and 31 P NMR spectroscopy for the title compound 9-diisopropylphosphinofluorenyl-lithium.

NMR:

1H (400.13 MHz, THF-d ₈ ), δ 7.85 (d, J = 7.5Hz, 2H), 7.75 (d, J = 7.9Hz, 2H), 6.83

(dt, J _! = 7.8Hz, J ₂ = l.lHz, 2H), 6.47 (t, J = 7.5Hz, 2H), 2.63 (m, 2H), 1.15 (dd, J _! = 15.2Hz, J ₂ = 6.9Hz, 6H), 0.92 (dd, J ^ 10 ^ Hz, J ₂ = 6.9Hz, 6H).

³¹ P (161.9 MHz, THF-d ₈ ), δ -6.57 ppm (singlet).

Example 18

Trimethylsilylbis (pentafluorophenyl) boranyl cyclopentadiene, (CH ₃ ) Si (C ₅ H4) B (C ₆ F5) 2 (Compound 18)

A suspension of Me ₃ Si (C ₅ H ₄ ) Li (4.20 g, 29.1 mmol) in 25 ml hexane was treated at -70 ° C. within 15 min with a solution of chlorobis (pentafluorophenyl) borane, C1B (C ₆ F ₅ ) ₂ , (11.09 g, 29.1 mmol) in 50 ml of hexane. The mixture was allowed to warm slowly to room temperature with stirring overnight. After filtering the yellow suspension, the solid was washed with hexane (5 ml x 2). After the volatile constituents had been stripped off from the filtrate under reduced pressure, a yellowish-brown gummy liquid remained, which slowly crystallized to yellowish-brown crystals (13.6 g, approx. 97%) within a few days at room temperature. 1H NMR (400.13 MHz, CD ₂ C1 ₂ ); δ main isomer: 7.61 (br. 1H), 7.10 (br. 1H), 7.00 (br. 1H), 4.9 (br. 1H), 0.00 (s, 9H). ^π B NMR (80.25 MHz, CD ₂ C1 ₂ ); δ 53.0 (br. s).

¹⁹ F NMR (376.3 MHz, CD ₂ C1 ₂ ); δ -130.6 (m, 4F), -152.0 (m, 2F), -162.6 (m, 4F).

1. a). R. Duchateau, S.J. Lancaster, M. Thornton-Pett and M. Bochmann.

Organometallics 1997, 16, 4995. b). M. Bochmann, S. J. Lancaster and O. B.

Robinson. J. Chem. Soc. Chem. Commun. 1995, 2081.

2. S.J. Lancaster, M. Thornton-Pett, D.M. Dowson and M. Bochmann.

Organometallics 1998, 77, 3829.

Example 19

Trimethylstannyl-2-methyl-bis (pentafluorophenyl) boranylinden,

(CH ₃ ) 3Sn-2-CH3- (C ₉ H5) B (C ₆ F5) 2 (Compound 19)

A solution of bis (trimethylstannyl) -2-methylindene, (Me ₃ Sn) ₂ -2-Me- (C ₉ H ₅ ), (3.29 g, 7.23 mmol) in 30 ml pentane was brought to -70 ° C cooled and added dropwise with a solution of bis (pentafluoropheny) boron chloride, C1B (C ₆ F ₅ ) ₂ , (2.75 g, 7.23 mmol) in 30 ml of pentane over a cannula within 20 minutes. A bright yellow slurry immediately formed. The mixture was kept at -70 ° C for 2 hours and allowed to warm slowly to 12 ° C overnight (14 hours). After the volatile components had been stripped off from the yellow slurry, the residue was used to sublimate Me ₃ SnCl for 5 hours

2.5 x 10 ^"3 mbar. The residue was taken up in 30 ml of pentane, redissolved and stored overnight in a freezer set to -30 ° C. The bright yellow crystals were filtered off and washed with cold pentane, which was 1.36 g of product (29.5%) was obtained in pure form, and a second fraction of 1.01 g (21.9%) was isolated from the concentrated cold mother liquor

(51% in total). Both fractions are spectroscopically pure. NMR:

^X H (400.13 MHz, CD ₂ C1 ₂ ); δ 7.38 (d, J = 7.6 Hz, 1H), 7.17 (t, J = 7.3 Hz, 1H), 7.05 (t, J = 7.1 Hz, 1H), 6.99 (d, J = 7.8 Hz, 1H), 4.85 (s, with Sn satellites due to coupling via two bonds, 1H), 2.26 (s, 3H), 0.18 (s, 9H).

^U B (128.4 MHz, CD ₂ C1 ₂ ); δ 54.1.

¹³ C (100.58 MHz, CD ₂ C1 ₂ ); δ 177.9, 146.2 (md, ¹ J _C - _F = 240.5 HZ), 144.4, 142.8,

142.6 (md, ¹ J _C - _F = 254.7 Hz), 138.2 (md, ^X 1 _C .Ϊ = 269.1 HZ), 124.6, 123.9, 121.2, 120.6, 63.7, 19.1, -7.5.

¹⁹ F (376.3 MHz, CD ₂ C1 ₂ ); δ -132.1 (dd, J. = 23 Hz, J ₂ = 9 Hz, oF), -153.0 (t, J = 20 Hz, pF), -162.4 (dt, Hz, mF).

Example 20

Bis (pentafluorophenyl) boranyI-2-methyl-trimethylstannyl-4-phenylene, [(F ₅ C6) 2B-2-CH3-4-C ₆ H5 (C ₉ H4) -Sn (CH ₃ ) 3 (compound 20)

A suspension of bis (trimethylstannyl) -2-methyl-4-phenylindene, (Me ₃ Sn) ₂ -2-Me-4-Ph- (C ₉ H ₄ ), (7.028 g, 13.2 mmol) in 40 ml A solution of bis (pentafluorophenyl) boron chloride, C1B (C ₆ F ₅ ) ₂ (5.026 g, 13.2 mmol) in 20 ml of dry pentane was added to dry pentane at -70 ° C. over a cannula within 30 min , The mixture (a pale yellow slurry) was stirred at -70 ° C for 260 minutes and then warmed to -30 ° C over 35 minutes. The volatiles were then removed under vacuum, keeping the temperature below -30 ° C. The yellow paste obtained was freed from the by-product trimethyltin chloride by vacuum treatment for 6 hours, 8.72 g

(92.6%) of a sticky yellow solid was obtained as a crude product. Example 21

Bis (pentafluorophenyI) boranylcyclopentadienyI zirconium trichloride, (C ₆ F ₅ ) ₂ B (C ₅ H ₄ ) ZrCl ₃ (Compound 21).

A suspension of ZrCl ₄ (1.92 g, 8.24 mmol) in 30 ml of toluene was treated at room temperature with a solution of trimethylsilyl-bis (pentafluorophenyl) boranyl-cyclopentadiene, Me ₃ Si (C ₅ H) B (C ₆ F ₅ ) ₂ , (4.0 g, 8.25 mmol) in 60 ml of toluene. The mixture was stirred under Ar overnight (16 h). After filtration of the suspension of pale yellow solid with toluene (2 x 5 mL), and the loose solid under a vacuum of 3 xlO ^"was mbar (3.88 g, 77.6%) up to constant weight.

NMR:

1H (400.13 MHz, d ₈ toluene); δ 6.87 (br. s), 6.51 (br. s), 6.46 (t, J = 2.5 Hz), 6.28 (t, J = 2.6Hz).

^π B (128.4 MHz, d ₈ toluene); δ 54.3 (broad signal at 65-45 ppm with maximum at 54.3 ppm).

¹⁹ F (376.3 MHz, d ₈ toluene); δ -127.3 (br. s), -128.4 (d, J = 19.9 Hz), -146.1 (br. s), -149.6 (d, J = 20.8 Hz), -160.0 (br. s), -161.3 ( t, J = 16.1 Hz). Example 22

l-bis (pentafluorophenyl) boranyl-2-methyl- (indenyI)] zirconium trichloride, [l- (C ₆ F5) 2B- (2-CH3-C ₉ H5) ZrCl3] (compound 22)

A suspension of zirconium tetrachloride, (ZrCl ₄ ) (2.84 g, 12.2 mmol) in 20 ml of toluene was treated at 0 ° C with a solution of trimethylstannyl-2-methyl-bis (pentafluorophenyl) boranylinden, (7, 89 g, 12.2 mmol) in 30 ml of toluene. The mixture was allowed to warm to room temperature and stirred overnight under an argon atmosphere. The cloudy orange solution obtained became

Separation of small insoluble parts filtered and the filtrate drawn dry. The orange solid was taken up in 30 ml of hexane, stirred for 30 minutes and then filtered through a cannula. The solid was then washed again with hexane (2 x 20 ml) and dried under vacuum to give 6.71 g (82%) of a loose orange-yellow solid.

NMR:

1H (400.13 MHz, CD ₂ C1 ₂ ), δ 7.88 (d, J = 8.2 Hz, 1H), 7.59 (m, 1H), 7.47 (m, 2H), 7.29 (s, 1H), 2.42 (s, 3H ).

^U B (128.4MHz, CD ₂ C1 ₂ ) δ 56.5 ppm (broad over a range of 45-65 ppm).

¹⁹ F (376.3MHz, CD ₂ C1 ₂ ) δ -128.9 (d, J = 18.4Hz, 4F, oF), -149.2 (t, J = 20Hz, 2F, pF), -160.6 (m, 4F, mF) , Example 23

[Bis (pentafluorophenyl) boranyl-2-methyl-4-phenylindenyl] zirconium trichloride,

[l- (F ₅ C ₆ ) ₂ B-2-CH ₃ -4-C ₆ Hs- (C ₉ H4) ZrCl ₃ ] (compound 23)

A suspension of zirconium tetrachloride, ZrCl ₄ , (2.85 g, 12.2 mmol) in 25 ml

Toluene was washed with a solution of the at room temperature within 10 min

Crude product of [bis (pentafluorophenyl) boranyl-2-methyl-trimethylstannyl-4-phenylindene], 1- (F ₅ C ₆ ) ₂ B-2-Me-3-Me ₃ Sn-4-Ph- (C ₉ H ₄ ), (8.72 g) in 35 ml of toluene. The mixture took on a red color and became under an argon atmosphere

Stirred for 16 hours. The orange-yellow suspension obtained was filtered through a cannula and the solid residue was washed with toluene (2 × 20 ml). The filtrate was combined with the wash solution and the volatiles were removed under reduced pressure to leave a sticky orange solid which was washed with dry hexane (2 x 15 ml) and filtered. After drying the

Solid under vacuum remained 2.0 g of an orange powder which contains the acceptor half-sandwich compound as a crude product.

Example 24

Dimethylphosphmo ~ cyclopentadienyl-bis (pentafluorophenyl) boranyl-cyclopentadienyl-zirconium dichloride,

[(C ₅ H4) (CH ₃ ) 2PB (C ₆ F5) 2 (C ₅ H4) ZrCl2] (compound 24)

A suspension of bis (pentafluorohenyl) boranyl-cyclopentadienylzirconium trichloride, [(C ₆ F ₅ ) ₂ B (C ₅ H ₄ ) ZrCl ₃ ], (0.963 g, 1.59 mmol) in 10 ml toluene was inside at room temperature a solution of trimethylsilyldimethylphosphinocyclopentadiene, Me ₃ Si (C ₅ H ₄ ) PMe ₂ , (0.315 g, 1.59 mmol) in 10 ml of toluene was added for 5 min. The mixture was heated to 80 ° C with an oil bath for 15 hours. The reaction mixture was cooled to room temperature and filtered through Celite to remove small insolubles. After the volatile components had been stripped off from the almost colorless filtrate, a whitish, dense crystalline remained Solid that loud ^! H NMR was 90% pure for the title compound. The product was washed with hexane (2 x 15 ml), dried under vacuum, resuspended in 15 ml of toluene and filtered through celite to give a slightly yellow solution. The solution was cooled to -35 ° C, and after standing for a few days in the cold, crystals slowly begin to grow. There were

0.76 g of crystalline solid obtained (68.6%).

NMR:

* H (400.13 MHz, CD ₂ C1 ₂ ); δ 6.85 (m, 4H), 6.73 (m, 2H), 6.33 (s, 2H), 1.91 (d,

J = 10.6Hz, 6H).

^π B (128.4 MHz, CD ₂ C1 ₂ ): δ -11.9 (broad d, J = 65 Hz).

¹³ C (100.58 MHz, CD ₂ C1 ₂ ); δ 148.0 (dm, J = 250Hz), 140.5 (dm, J = 244.6Hz),

137.9 (dm, J = 258.7Hz), 124.6 (d, J = 7Hz), 123.3, 122.2, 118.5 (d, J = 8Hz), 110.4 (d, J = 65.0Hz), 14.2 (d, J = 36.2Hz).

¹⁹ F (376.3 MHz, CD ₂ C1 ₂ ); δ -128.2 (d, J = 23Hz, 4F, oF), -156.9 (t, J = 21Hz, 2F, pF), -163.1 (m, 4F, mF).

³¹ P (161.9 MHz, CD ₂ C1 ₂ ); δ 2.7 ().

Example 25

Diethylphosphino-cyclopentadienyl-bis (pentafluorophenyl) boranyl-cyclopentadienyl-zirconium dichloride,

[(C5H4) (C ₂ H ₅ ) 2PB (C ₆ F ₅ ) ₂ (C ₅ H4) ZrCl2] (compound 25)

A suspension of bis (pentafluorophenyl) boranyl-cyclopentadienylzirconium trichloride, [(C ₆ F ₅ ) ₂ B (C ₅ H ₄ ) ZrCl ₃ ], (4.18 g, 6.89 mmol) in 60 ml of toluene was added at room temperature over a cannula within 25 min. with a solution of trimethylsilyl-diethylphosphino-cyclopentadiene, Me ₃ Si (C ₅ H) PEt ₂ , (1.50 g. 6.63 mmol) in 20 ml of toluene. The mixture was heated in a 100 ° C oil bath for 24 hours. The slightly cloudy solution obtained was cooled to room temperature and filtered through Celite. The off-white crystalline solid remaining after stripping volatiles from the clear and colorless filtrate under reduced pressure was washed with hexane (2 x 20 ml) and dried under vacuum to give 3.77 g (78.5%) of a white solid. The product, which was essentially pure according to NMR, was redissolved in as little toluene as possible and hexane was added to the clear solution until it became cloudy and the mixture was cooled to -35 ° C. for a few weeks. A microcrystalline powder slowly separated from the container wall. The supernatant was decanted off and the product dried under vacuum. The product was pure by NMR spectroscopy.

NMR:

1H (400.13 MHz, CD ₂ C1 ₂ ); δ 6.84 (4H), 6.76 (2H), 6.29 (2H), 2.56 (m, 2H), 2.18 (m, 2H), 1.06 (m, 6H).

^U B (128.4 MHz, CD ₂ C1 ₂ ): δ -11.9 (d, J = 67Hz)

¹⁹ F (376.3 MHz, CD ₂ C1 ₂ ); δ -127.8 (d, J = 20 Hz, 4F, oF), -157.1 (t, J = 19 Hz, 2F, pF), -163.2 (m, 4F, mF).

³¹ P (161.9 MHz, CD ₂ Cl ₂ ); δ 14.3 (m). Example 26

Diisopropylphosphino-cyclopentadienyl-bis (pentafluorophenyl) boranyl-cyclopentadienyl-zirconium dichloride, [(C ₅ H4) {(CH3) ₂ CH} ₂ PB (C ₆ F ₅ ) 2 (C ₅ H4) ZrCl ₂ ] (compound 26)

A suspension of bis (pentafluorophenyl) boranyl-cyclopentadienylzirconium trichloride, (C ₆ F ₅ ) ₂ B (C ₅ H ₄ ) ZrCl ₃ , (3.80 g, 6.26 mmol) in 50 ml of toluene was added at room temperature Cannula within 20 min. With a solution of trimethylsilyl-diisopropylphosphino-cyclopentadiene, Me ₃ Si (C ₅ H ₄ ) P (CHMe ₂ ) ₂ , (1.59 g,

6.25 mmol) in 20 ml of toluene. The clear orange-red solution obtained was heated with an oil bath at 100 ° C. for 24 hours, a slightly cloudy, light yellow solution being obtained. The reaction mixture was cooled to room temperature and filtered through Celite to remove small insolubles. After the volatiles were stripped off from the filtrate under reduced pressure, an off-white crystalline solid remained. The solid was washed with dry hexane (2 x 10 ml) and dried under vacuum to give 4.01 g of a white powder (85%). The product was dissolved in the smallest possible amount of toluene and left to stand at room temperature for two days, whereupon crystals began to grow. The solution was then kept in a 4 ° C. refrigerator for two weeks, after which the crystals which were suitable for the X-ray structure examination were filtered off. The unit cell contains four molecules in different conformations, all of which are PB-bridged. d (PB) = 2.05 - 2.11 angstroms.

Example 27

Diphenylphosphino-cyclopentadienyl-bis (pentafiuorphenyl) boranyl-cyclopentadienyl-zirconium dichloride,

[(C ₅ H ₄ ) (C6H ₅ ) 2PB (C ₆ F ₅ ) 2 (C ₅ H4) ZrCl ₂ ] (Compound 27)

A suspension of bis (pentafluorophenyl) boranyl-cyclopentadienylzirconium trichloride, (2.25 g, 3.71 mmol) in 25 ml of toluene was treated at room temperature with a solution of trimethylsilyl-diphenylphosphino-cyclopentadiene, (1.16 g, 3.61 mmol) added in 13 ml of toluene. The mixture was heated to 110 ° C with an oil bath for 24 hours. The slightly cloudy reaction solution was cooled to room temperature and filtered through Celite to remove small insoluble fractions. After the volatiles had been stripped off from the clear filtrate under reduced pressure, a whitish powdery solid remained, which was mixed with hexane (2 ×

15 ml) and then washed with toluene (15 ml) and dried under vacuum to give 2.53 g of a white powder (85%). According to NMR, the product is pure.

NMR: 1H (400.13 MHz, CD ₂ C1 ₂ ); δ wide resonances between 7.6 and 6.2 ppm,

Reference to dynamic processes in solution.

ⁿ B (128.4 MHz, CD ₂ C1 ₂ ): δ -7.9.

³¹ P (161.9 MHz, CD ₂ C1 ₂ ): δ 22.4.

Example 28

l-dimethylphosphino-2-methylindenyl-bis (pentafluorophenyl) boranylcyclopentadienyl zirconium dichloride,

[(2-CH ₃ -C ₉ H ₅ ) (CH ₃ ) 2PB (C ₆ F5) 2 (C ₅ H4) ZrCl2] (Compound 28)

A suspension of bis (pentafluorophenyl) boranylcyclopentadienylzirconium trichloride, (C ₆ F ₅ ) ₂ BCpZrCl ₃ , (2.08 g, 3.43 mmol) in 30 ml of toluene was dissolved at 0 ° C. in the course of 15 minutes with a solution of 1 -Trimethylstannyl-2-methyl-3-dimethylphosphinoindene, l-Me ₃ Sn-2-Me-3-Me ₂ P (C ₉ H ₅ ), (1.18 g, 3.34 mmol) in 23 ml of toluene added. The cloudy yellow mixture obtained was stirred under argon at room temperature for 16 hours. The slightly cloudy solution was filtered through Celite and freed from volatiles under reduced pressure, leaving a yellow solid which was taken up in 20 ml of hexane and stirred for 20 minutes.

The fine suspension was filtered and the solid twice more with hexane (2 x 20 ml) washed. Drying the solid under vacuum gave 2.40 g of substance (94%).

NMR:

1H (400.13 MHz, CD ₂ C1 ₂ ): δ 7.74 (d, J = 8.52 Hz, 1H), 7.68 (d, J = 8.94Hz, 1H), 7.46 (m, 1H), 6.82 (d, J = 2.45 Hz, 1H), 6.62 (m, 1H), 6.52 (m, 1H), 6.31 (s, 1H), 5.98 (s, 1H), 2.51 (s, 3H), 2.13 (d, J = 10.75Hz, 3H ), 2.03 (d, J = 10.55Hz, 3H).

^U B (128.4 MHz, CD ₂ C1 ₂ ): δ -9.68 ppm (d, J = 56.8 Hz).

¹⁹ F (376.3MHz, CD ₂ C1 ₂ ): δ -126.2 (s, 2F), -126.6 (s, 2F), -157.1 (m, 2F), -162.9 (m, 4F).

³¹ P (161.9MHz, CD ₂ C1 ₂ ): δ 10.48 ppm.

Example 29

l-diethylphosphino-2-methyl-indenyl-bis (pentafluorophenyl) boranyl-cyclopentadienyl-zirconium dichloride, [2-CH ₃ -C ₉ H ₅ (C ₂ H ₅ ) 2PB (C ₆ F5) 2 (C2H4) ZrCl2] (Connection 29)

A solution of l-trimethylstannyl-2-methyl-3-diethylphosphino (inden), l-Me ₃ Sn- 2-Me-3-Et ₂ P- (C ₉ H ₅ ), (0.476 g, 1.25 mmol) in 15 ml of toluene at room temperature within 10 minutes to a suspension of bis (pentafluorophenyl) boranylcyclopentadienylzirconium trichloride, (C ₆ F ₅ ) ₂ B (C ₅ H ₄ ) ZrCl ₃ , (0.758 g, 1.25 mmol) in Given 15 ml of toluene. The cloudy solution was stirred for 18 hours, after which the slightly cloudy solution was filtered through Celite to remove small insoluble fractions. The filtrate was pulled dry under reduced pressure.

The yellow solid was taken up in 20 ml of hexane and stirred for 30 minutes. The suspension was filtered and the solid washed with pentane (2 x 10 ml) and dried under vacuum to yield 0.837 g (85%) of yellow powdery product. The product is pure by NMR spectroscopy.

NMR:

1H (400.13MHz, C ₆ D ₆ ): δ 7.45 (d, J = 7.72Hz, 1H), 7.28 (d, J = 8.41Hz, 1H), 7.06 (t, J = 7.18Hz, 1H), 6.72 ( t, J = 8.14Hz, 1H), 6.46 (m, 1H), 6.35 (m, 2H), 6.12 (s, 1H), 5.75 (s, 1H), 2.20 (m, 1H), 2.07 (s, 3H) ), 2.02 (m, 1H), 1.78 (m, 2H), 0.26 (m, 6H).

ⁿ B (128.4MHz, C ₆ D ₆ ): δ -9. LPPM.

¹⁹ F (376.3MHz, C ₆ D ₆ ): δ -124.9 (d, J = 13.5Hz, 2F, oF), -125.2 (d, J = 13.2Hz, 2F, oF), -155.4 (t, J = 21.8Hz, 1F, pF), -155.7 (t, J = 21.0Hz, 1F, pF), -162.1 (m, 4F, mF).

³¹ P (161.9MHz, C ₆ D ₆ ): δ 28.1 ppm.

Example 30

l-Dimethylphosphino-2-methyl-indenyl-l'-bis (pentafluorophenyl) boranyl-2'-methyl-indenyl-zirconium dichloride, [(2-CH3-C ₉ H ₅ ) - (CH3) 2PB (C ₆ F5) 2 - (2-CH3-C ₉ H5) ZrCl2] (compound 30)

A suspension of l-bis (pentafluorophenyl) boranyl-2-methylindenylzirconium trichloride, [l- (C ₆ F ₅ ) ₂ B-2-Me- (C ₉ H ₅ ) ZrCl ₃ ], (1.136 g, 1.69 mmol) in 30 ml of toluene was cannulated at room temperature within 10 minutes with a solution of 1-trimethylstannyl-2-methyl-3-dimethylphosphino-indene, 1-Me ₃ Sn-2-Me-3-Me ₂ PC ₉ H ₅ , (0.598 g, 1.69 mmol) in 18 ml of toluene. The slightly cloudy solution was heated with a 60 ° C. oil bath with stirring for 6 hours. A large amount of a yellow solid was formed. The reaction mixture was cooled to room temperature and the supernatant was filtered through a cannula into another Schlenk tube. The solid was washed with toluene (3 x 5 ml) and hexane (2 x 5 ml) Washed, after which the washing solutions were combined with the filtrate. The remaining solid was dried under vacuum to give 0.71 g (50.8%) of a light yellow microcrystalline solid. The NMR spectra of this solid in CD ₂ C1 ₂ show mainly rac isomer (rac isomer: meso isomer = 90:10). The filtrate combined with the wash solutions was pulled dry, washed with hexane (2 x 20 ml) and dried under vacuum to give 0.67 g (48%) of a yellow powdery product. The NMR spectra in CD ₂ C1 ₂ show mainly meso isomer (rac isomer: meso isomer = 20:80). The overall yield of the reaction is more than 98% and under these reaction conditions the ratio of rac to meso is 62:38.

NMR:

1H (400.13MHz, CD ₂ C1 ₂ ): rac isomer δ 7.71 (d, J = 8.7Hz, 1H), 7.55 (m, 2H), 7.38 (m, 2H), 7.26 (d,

J = 7.6Hz, 1H), 7.05 (m, 1H), 6.73 (s, 1H), 6.65 (d, J = 2.1Hz, 1H), 2.26 (d, broadened J = 10.7Hz, 6H), 2.24 (s , 3H), 1.70 (s, 3H).

meso isomer δ 7.71 (d, J = 8.6Hz, 1H), 7.47 (d, J = 8.5Hz, 1H), 7.40 (d,

J = 8.5Hz, 1H), 7.26 (t, J = 6.7Hz, 1H), 7.04 (t, J = 8.0Hz, 2H), 6.79 (s, 1H), 6.60 (s, 1H), 6.56 (s, 2H), 2.59 (s, 3H), 2.43 (s, 3H), 2.27 (dd, J = 9.8Hz, 6H).

^U B (128.4MHz, CD ₂ C1 ₂ ): rac isomer δ -7.09 (singlet). meso isomer δ -7.04 (singlet).

¹⁹ F (376.3MHz, CD ₂ C1 ₂ ): rac isomer δ -124.6 (m, 1F, oF), -127.2 (broad s, 2F, oF), -128.6 (m,

1F, oF), -157.3 (t, J = 20.8Hz, 1F, pF), -157.6 (t, J = 20.5Hz, 1F, pF), -161.8 (m, 1F, mF), -163.0 (m, 2F, mF), -163.7 (m, 1F, mF). meso isomer δ -124.2 (m, 1F, oF), -127.6 (broad, 3F, oF), -157.4 (m, 2F, p-F), -161 to -163 (broad, 4F, mF).

³¹ P (161.9MHz, CD ₂ C1 ₂ ), rac isomer δ 18.9 (broad multiplet). , meso isomer δ 17.75 (broad multiplet).

Example 31

9-diethylphosphinofluorenylbis (pentafluorophenyl) boranylcyclopentadienyl zirconium dichloride,

[(Ci ₃ H ₈ ) (C ₂ H ₅ ) ₂ Et ₂ PB (C ₆ F ₅ ) ₂ (C ₅ H ₄ ) ZrCl ₂ ] (compound 31)

A suspension of 9-diethylphosphinofluorenyllithium, Li [9-Et ₂ P- (C ₁₃ H ₈ )], (0.235 g, 0.903 mmol) in 15 ml of toluene was cannulated at room temperature within 10 minutes with a solution of Bis (Pentafluorophenyl) boranyl-cyclopentadienyl-zirconium trichloride, (F ₅ C ₆ ) ₂ BCpZrCl ₃ , (0.548 g, 0.903 mmol) in 25 ml of toluene. The mixture turned brownish-red when the addition was complete.

After stirring overnight under an Ar atmosphere, the cloudy solution was filtered through Celite to remove LiCl. The clear orange-red solution was pulled dry, leaving a dense orange solid which was washed with pentane (2 x 15 ml) and dried. This gave 0.71 g (95%) of a dense yellowish-orange microcrystalline solid. According to NMR analysis, this was the title compound.

NMR spectroscopic characterization: 1H (400.13 MHz, C ₆ D ₆ ), δ 7.94 (d, J = 8.3Hz, 2H), 7.53 (d, J = 8.6Hz, 2H), 7.45 (pseudo-t, J = 7.7Hz, 2H), 7.19 (pseudo-t, J = 8.3Hz, 2H), 6.37 (m, 2H), 6.06 (s, 2H), 2.42 (m, 2H), 2.04 (m, 2H), 0.38 (m, 6H).

^U B (128.4 MHz, C ₆ D ₆ ), δ -9.3 (br.s).

¹⁹ F (376.9 MHz, C ₆ D ₆ ), δ -125.2 (d, J = 22Hz, 4F, oF), -155.5 (t, J = 21Hz, 2F, p- F), -162.2 (t, J = 22Hz, 4F, mF).

³¹ P (161.9 MHz, C ₆ D ₆ ), δ 35.1 (br.s.).

Example 32

9-diethylphosphinofluorenyl-1-bis (pentafluorophenyl) boranyl-2-methylindenyl zirconium dichloride,

[(C ₁₃ H ₈ ) - (C2H5) 2PB (C ₆ F5) 2- (2-CH3-C ₉ H ₅ ) ZrCl2] (compound 32)

A suspension of 9-diethylphosphinofluorenyllithium, Li [9-Et ₂ P- (C ₁₃ H ₈ )], (0.29 g, 1.11 mmol) in 15 ml of toluene was mixed at room temperature with a cannula within 10 min a solution of l-bis (pentafluorophenyl) boranyl-2-methylindenyl-zirconium trichloride, [l- (F ₅ C ₆ ) ₂ B-2-Me- (C ₉ H ₅ ) ZrCl ₃ ], (0.75 g, 1 , 11 mmol) in 30 ml of toluene. The orange-red suspension was stirred under an Ar atmosphere overnight and then filtered through Celite, after which the solid was washed with CH ₂ C1 for better dissolution of the product. The orange residue remaining after drying the combined filtrates was washed with pentane (3 x 15 ml). The orange powder was dried under high vacuum (1.0 x 10 ^"3 mbar), leaving 0.81 g (82%) of product in the form of orange powder. According to NMR spectroscopic analysis, this was the title compound, [(-C ₃ H ₈ ) -9-Et ₂ PB (C ₆ F5) 2-2-Me- (C ₉ H ₅ ) ZrCl2].

NMR spectroscopic characterization: 1H (400.13 MHz, C ₆ D ₆ ), δ 7.75 (t, J = 8.7Hz, 2H), 7.66 (d, J = 8.2Hz, 1H), 7.50 (t,

J = 8.5Hz, 2H), 7.43 (d, J = 8.9Hz, 1H), 7.34 (d, J = 8.4Hz, 1H), 7.29 (d,

J = 8.4Hz, 1H), 7.17 (t, J = 8.3Hz, 1H), 6.99 (t, J = 8.3Hz, 1H), 6.97 (t, J = 8.1Hz, 1H), 6.76 (t, J = 7.8Hz, 1H), 6.60 (s, 1H), 2.93-2.87 (m, 1H), 2.63-2.43 (m,

3H), 0.65 (m, J = 7.3Hz, 3H), 0.52 (m, 3H).

^U B (128.4 MHz, C ₆ D ₆ ), δ -6.20 ppm (broad singlet).

¹⁹ F (376.3 MHz, C ₆ D ₆ ), δ -126.3 (s, 3F, oF), -130.1 (m, 1F, oF), -155.7 (m, 2F, pF), -160.5 (m, 1F, mF), -162.2 (s, 3F, mF).

³¹ P (161.9 MHz, C ₆ D ₆ ), δ 45.3 ppm (br.s.).

Example 33

l-diethylphosphino-2-methyl-4-phenyl (indenyl) -l-bis (pentafluorophenyl) boranyl-2-methyl-4-phenyl (indenyl) zirconium dichloride,

[(2-CH3-4-C ₆ H5-C ₉ H4) - (C2H ₅ ) 2PB (C ₆ F ₅ ) ₂ - (2-CH3-4-C ₆ H5-C ₉ H ₄ ) ZrCl2] (compound 33)

A solution of the acceptor half-sandwich raw product bis (pentafluoφhenyl) boranyl-2-methyl-4-phenylindenylzirconium trichloride, (0.655 g) in 10 ml of toluene was added dropwise at room temperature in the course of 10 minutes with a solution of l-diethylphosphino-2-methyl-3-trimethylstannyl-4-phenylindene,

(l-Et ₂ P-2-Me-3-Me ₃ Sn-4-Ph-C ₉ H ₄ ), (0.404 g, 0.877 mmol) in 10π toluene. The mixture immediately became cloudy and a large amount of an orange precipitate formed after the addition was complete. The mixture was stirred at room temperature for 16 hours. The suspension was then filtered and the solid washed with toluene (2 x 6 ml). The filtrate combined with the wash solutions was pulled dry to give a solid which was taken up in 15 ml of dry hexane and filtered after stirring for 15 min. The orange solid was then washed further with hexane (2 x 6 ml) and filtered. The solid residue was dried under high vacuum to give 0.46 g of an orange powder. This crude product of the title compound was used for the polymerization without purification.

Example 34

Ethene polymerization

A dry, oxygen-free 300 ml V4A steel autoclave was charged with 100 ml of dry toluene, which had been distilled under an inert gas, and the catalyst was added at 60 ° C. using an injection syringe. 5xl0 ^"8 mol served as catalyst

[(cp) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (Compound No. 25) in 0.33 ml of a 10% toluene MAO solution (0.5 mmol). A constant 10 bar was set with ethene. The polymerization ran in the temperature range 60 ° to 72 ° C and was stopped after 30 minutes. The polyethene formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and to constant weight in

Vacuum drying cabinet dried at 80 ° C.

Polymer yield: 3.7 g

Catalyst activity: 148 tons PE per mol Zr and hour

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 3.56 dl / g

GPC: (universal calibration using M _w = 356 kg / mol of polystyrene standards) M _n = 141 kg / mol

DSC: (2nd heating) Melting temperature: T _m = 139 ° C

Enthalpy of fusion: H _m = 176 J / g Example 35

Ethene polymerization

In a dry, oxygen-free 300 ml V4A steel autoclave, 100 n dry toluene destilled under an inert gas were placed and the catalyst was added at 80 ° C. using an injection syringe. The catalyst used was 1x10 ^" m <[(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound No. 31) in 0.66 ml of a 10% toluene MAO solution (1 mmol) A constant 10 bar was set with ethene. The polymerization ran in the temperature range from 80 ° to 88 ° C. and was

Minutes canceled. The polyethylene formed was stirred with ethanol / hydrochloric acid 90/1, filtered, washed with ethanol and dried to constant weight in a vacuum drying cabinet at 80 ° C.

Polymer yield: 2.9 g

Catalyst activity: 58 tons PE per mol Zr and hour

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 7.86 dl / g

GPC: (universal calibration using M _w = 1306 kg / mol of polystyrene standards) M _n = 102 kg / mol

High temperature GPC / Niscosimetry coupling: The polymer is long-chain branched.

DSC: (2nd heating) Melting temperature: T _m = 139 ° C

Enthalpy of fusion: H _m = 166 J / g Example 36

Ethene polymerization

A dry, oxygen-free 300 ml V4A steel autoclave was charged with 100 n dry toluene, which had been distilled under an inert gas, and the catalyst was added at 60 ° C. using an injection syringe. The catalyst used was 1x10 ^" mc [(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound no. 31) in 0.66 ml of a 10% toluene MAO solution (1 mmol). The polymerization was set at a constant 10 bar with ethene and the polymerization was carried out in the temperature range from 60 ° -66 ° C. and was stopped after 30 minutes, and the polyethene formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and brought to constant weight in Vacuum drying cabinet dried at 80 ° C.

Polymer yield: 2.6 g

Catalyst activity: 52 tons of PE per mole of Zr and hour

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 13.25 dl / g

GPC: (universal calibration using M _w = 11120 kg / mol of polystyrene standards) M _n = 1420 kg / mol

High temperature GPC / Niscosimetry coupling: The polymer is branched long chain.

DSC: (2nd heating) Melting temperature: T _m = 137 ° C

Enthalpy of fusion: H _m = 139 J / g Example 37

Propene polymerization

In a dry, oxygen-free 300 ml V4A steel autoclave approx. 1 m

Propene submitted and the polymerization in bulk at 20 ° C started by catalyst addition by means of a pressure lock. Lxl 0 ^"6 mol [(2-M md) Me ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound no. 28) in 6.6 ml of a 10% igι toluo fish MAO- Solution (10 mmol) The polymerization ran in the temperature range 20 ° -25 ° C. and was terminated after 30 minutes The polypropene formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol g and until constant weight in Vacuum drying cabinet dries at 80 ° C g.

Polymer yield: 14.4 g

Catalyst activity: 28.8 tons of PP per mole of Zr and hour.

NMR (triad analysis): 37% isotactic

41% atactic 22% syndiotactic

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 1.13 dl / g

GPC: (universal calibration using M _w = 157 kg / mol of polystyrene standards) M _n = 88 kg / mol

DSC: (2nd heating) amorphous PP T _g = -4 ° C Example 38

Propene polymerization

In a dry, oxygen-free 300 ml V4A steel autoclave approx. 1 mc

Propene submitted and the polymerization in bulk at 20 ° C started by adding catalyst using a pressure lock. Lxl 0 ^"6 mol rac - [(2-M. Ind) Me ₂ PB (C ₆ F ₅ ) ₂ (2-Me-ind) ZrCl ₂ ] (compound no. 30-rac) in 1 ml of a served as catalyst Immolar toluene TIBA solution (100 μmol) and 4 μmol N, N-dimethylaniliniun tetrakispentafluorophenylborate in toluene (1 μmol / 1 ml). The polymerization proceeded ii

Temperature range 20 ° -25 ° C and was canceled after 30 minutes. The g. The polypropene formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed in ethanol and dried to constant weight in a valine drying oven at <80 ° C.

Polymer yield: 4.6 g

Catalyst activity: 9.2 tons of PP per mole of Zr per hour

NMR (triad analysis): 93% isotactic 5% atactic

2% syndiotactic

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 4.38 dl / g

GPC: (universal calibration using M _w = 1289 kg / mol of polystyrene standards) M _n = 313 kg / mol

DSC: (1st heating) Melting temperature: T _m = 156 ° C

Enthalpy of fusion: H _m = 115 J / g (2nd heating) melting temperature: T _m = 151 ° C

Enthalpy of fusion: H _m = 101 J / g Example 39

Propene polymerization

In a dry, oxygen-free 300 ml V4A steel autoclave, approx. 1 mol

Propene submitted and started at about 55 ° C in bulk polymerization by adding catalyst using a pressure lock. 0.974 mg rac- [(2-Me-4-Ph-ind) Et ₂ PB (C ₆ F ₅ ) ₂ (2-Me-4-Ph-ind) ZrCl ₂ ] served as the catalyst (from Example 33) in 6.6 ml of a 10% toluene MAO solution (10 mmol). The polymerization ran in the temperature range 55 ° -60 ° C and was stopped after 30 minutes. The polypropene formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and dried to constant weight in a vacuum drying cabinet at 80 ° C.

Polymer yield: 20.3 g

NMR (triad analysis): 99% isotactic

1% atactic

0% syndiotactic

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 2.01 dl / g

DSC: (2nd heating) Melting temperature: T _m = 161 ° C

Enthalpy of fusion: H _m = 92 J / g

With a corresponding polymerization carried out in the temperature range 68 ° -72 ° C, the measured intrinsic viscosity in ODCB (ortho-dichlorobenzene at 140 ° C) was still 1.95 dl / g and the DSC measurement (2nd heating) showed a melting maximum T _m = 161 ° C. Example 40

Propene polymerization

Approx. 1 mol of propene was placed in a dry, oxygen-free 300 ml V4A steel autoclave and the bulk polymerization was started at 20 ° C. by adding a catalyst using a pressure lock. Lxl 0 ^"6 mol [(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound no. 31) in 6.6 ml of a 10% toluene MAO solution (10 mmol The polymerization was carried out in the temperature range of 20 ° -24 ° C. and was stopped after 30 minutes The polypropene formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and to constant weight in a vacuum drying cabinet at 80 ° C. dried.

Polymer yield: 8.3 g

Catalyst activity: 16.6 tons of PP per mole of Zr per hour

NMR (triad analysis): 15% isotactic

41% atactic

45% syndiotactic

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 2.78 dl / g

GPC: (universal calibration using M _w = 534 kg / mol of polystyrene standards) M _n = 236 kg / mol

High temperature GPC / viscometry coupling: The polymer is branched by long chains

DSC: (2nd heating) amorphous PP -1 ° C Example 41

Propene polymerization

Approx. 1 mol of propene was placed in a dry, oxygen-free 300 ml V4A steel autoclave and the bulk polymerization was started at 20 ° C. by adding a catalyst using a pressure lock. Lxl0 ^"6 mol [(flu) Et ₂ PB (C ₆ F5) ₂ (2-Me-ind) ZrCl ₂ ] (compound no. 32) in 6.6 ml of a 10% toluene MAO solution ( The polymerization ran in the temperature range 20 ° -23 ° C. and was stopped after 60 minutes, the polypropene formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and to constant weight in a vacuum drying cabinet at 80 ° C. dried.

Polymer yield: 14.5 g catalyst activity: 14.5 tons of PP per mol Zr and hour

NMR (triad analysis): 68% isotactic

21% atactic

11% syndiotactic

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 1.04 dl / g

DSC: (2nd heating) Glass transition temperature: T _g = -6 ° C

Melting peak: T _m = 148 ° C. Melting enthalpy: H _m = 32 J / g Example 42

Ethene propene copolymerization

100 ml of dry toluene and 10 g of propene distilled under inert gas were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At an internal temperature of 40 ° C the pressure was increased from 3 bar with ethene to 4 bar. 2.5x10 ^"7 mol [(cp) Me ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound no. 24) in 0.25 ml of an molar toluene TIBA solution (25 μmol) served as the catalyst. and 1 μmol of N, N-dimethylanilinium tetrakispentafluorophenylborate in chlorobenzene (1 μmol / 1ml). The catalyst was added via a pressure lock and the pressure was increased from 4 bar to 5 bar. The polymerization ran in the temperature range from 40 ° -44 ° C. and Minutes canceled.

The polymer formed was stirred with ethanol / hydrochloric acid 90/10, filtered, with

Washed ethanol and dried to constant weight in a vacuum drying cabinet at 80 ° C.

Polymer yield: 3.5 g catalyst activity: 28.0 tons of EP rubber per mol Zr and hour

FTIR: propene: 55% by weight ethene: 45% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 2.12 dl / g

GPC: (universal calibration using M _w = 193 kg / mol of polystyrene standards) M _n = 106 kg / mol

DSC: amorphous copolymer T _g = -57 ° C Example 43

Ethene propene copolymerization

100 ml of dry toluene and 10 g of propene distilled under inert gas were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At an internal temperature of 40 ° C the pressure was increased from 3 bar with ethene to 4 bar. 2.5x10 ^"7 mol [(2-Me-ind) Me ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound no. 28) in 1.65 ml of a 10% toluene MAO served as catalyst Solution (2.5 mmol) The catalyst was added via a pressure lock and the pressure was increased from 4 bar to 5 bar The polymerization ran in the temperature range from 40 ° to 44 ° C. and was stopped after 30 minutes.

The polymer formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and added to constant weight in a vacuum drying cabinet

80 ° C dried.

Polymer yield: 5.2 g catalyst activity: 41.6 tons of EP rubber per mol Zr and hour

FTIR: propene: 41% by weight

Ethene: 59% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 2.29 dl / g

GPC: (universal calibration using M _w = 243 kg / mol of polystyrene standards) M _n = 94 kg / mol

DSC: (2nd heating) Glass transition temperature: T _g = -57 ° C enthalpy of fusion: H _m = 23 J / g Example 44

Ethene propene copolymerization

100 ml of dry toluene and 10 g of propene distilled under inert gas were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At an internal temperature of 20 ° C, the pressure was increased from 2 bar with ethene to 3 bar. 2.5x10 ^"7 mol rαc - [(2-Me-md) Me ₂ PB (C ₆ F ₅ ) ₂ (2-Meind) ZrCl ₂ ] (compound no. 30-rac) and 1, 65 ml of a 10% toluene MAO solution (2.5 mmol) The catalyst was added via a pressure lock and the pressure was increased from 3 bar to 4 bar The polymerization ran in the temperature range from 20 ° -23 ° C. and was after 30 Minutes canceled.

The polymer formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and added to constant weight in a vacuum drying cabinet

80 ° C dried.

Polymer yield: 5.9 g catalyst activity: 47.2 tons of EP rubber per mol Zr and hour

FTIR: propene: 63% by weight ethene: 37% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 2.33 dl / g

GPC: (universal calibration using M _w = 272 kg / mol of polystyrene standards) M _n = 125 kg / mol

DSC: (2nd heating) Glass transition temperature: T _g = -59 ° C

Enthalpy of fusion: H _m = 7 J / g

Melting peak: T _m = -29 ° C Example 45

Ethene propene copolymerization

100 ml of dry toluene and 10 g of propene distilled under inert gas were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At an internal temperature of 20 ° C, the pressure was increased from 2 bar with ethene to 3 bar. The catalyst used was 5 × 10 ⁷ mol [(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cρ) ZrCl ₂ ] (compound No. 31) and 3.3 ml of a 10% toluene MAO solution (5 mmol) The catalyst was added via a pressure lock and the pressure was increased from 3 bar to 4 bar The polymerization ran in the temperature range from 20 ° -24 ° C. and was stopped after 30 minutes.

The polymer formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and added to constant weight in a vacuum drying cabinet

80 ° C dried.

Polymer yield: 8.0 g catalyst activity: 32.0 tons of EP rubber per mol Zr and hour

FTIR: propene: 89% by weight ethene: 11% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 2.76 dl / g

GPC: (universal calibration using M _w = 467 kg / mol of polystyrene standards) M _n = 104 kg / mol

High temperature GPC / viscometry coupling: The polymer is branched by long chains.

DSC: amorphous copolymer T _e = -36 ° C / -16 ° C Example 46

Ethene propene copolymerization

100 ml of dry toluene and 10 g of propene distilled under inert gas were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At an internal temperature of 40 ° C, the pressure was increased from 3 bar with ethene to 4 bar. 2.5x10 ^"7 mol [(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound no. 31) and 1.65 ml of a 10% toluene MAO solution (2nd , 5 mmol) The catalyst was added via a pressure lock and the pressure was increased from 4 bar to 5 bar The polymerization ran in the temperature range 40 ° -44 ° C. and was stopped after 30 minutes.

The polymer formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and added to constant weight in a vacuum drying cabinet

80 ° C dried.

Polymer yield: 5.6 g catalyst activity: 44.8 tons of EP rubber per mole Zr and hour

FTIR: propene: 79% by weight ethene: 21% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 3.02 dl / g

GPC: (universal calibration using M _w = 422 kg / mol of polystyrene standards) M _n = 173 kg / mol

High temperature GPC / viscometry coupling: The polymer is branched by long chains.

DSC: amorphous copolymer T _g = -38 ° C / -24 ° C Example 47

Ethene propene copolymerization

100 ml of dry toluene and 10 g of propene distilled under inert gas were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At an internal temperature of 40 ° C, the pressure was increased from 3 bar with ethene to 5 bar. 2.5xl0 ^"7 mol [(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (Nerbinding Νr. 31) and 1.65 ml of a 10% toluene MAO solution (2nd , 5 mmol) The catalyst was added via a pressure lock and the pressure was increased from 5 bar to 7 bar The polymerization ran in the temperature range 40 ° -48 ° C. and was stopped after 30 minutes.

The polymer formed was stirred with ethanol / hydrochloric acid 90/10, filtered, washed with ethanol and added to constant weight in a vacuum drying cabinet

80 ° C dried.

Polymer yield: 5.7 g catalyst activity: 45.6 tons of EP rubber per mol Zr and hour

FTIR: propene: 65% by weight ethene: 35% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 4.35 dl / g

GPC: (universal calibration using M _w = 659 kg / mol of polystyrene standards) M _n = 248 kg / mol high-temperature GPC / nicosimetry coupling: the polymer is long-chain branched.

DSC: amorphous copolymer T ₂ = -51 ° C Example 48

Ethene propene ethylidenenorbornene terpolymerization

100 ml of dry toluene distilled under inert gas, 10 g of propene and 2 g of 5-ethylidene-2-norbornene were placed in a dry, oxygen-free 300 ml N4A steel autoclave. At an internal temperature of 80 ° C, the pressure was increased from 5.5 bar with ethene to 7.5 bar. 2.5x10 ^" mol [(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound Νr. 31) and 1.65 ml of a 10% toluene MAO solution (2, 5 mmol) The catalyst was added via a pressure lock and the pressure was increased from 7.5 bar to 9.5 bar The polymerization ran in the temperature range from 80 ° -82 ° C. and was terminated after 30 minutes / Hydrochloric acid 90/10, filtered, washed with ethanol and dried to constant weight in a vacuum drying cabinet at 80 ° C.

Polymer yield: 5.4 g catalyst activity: 43.2 tons of EP rubber per mol Zr and hour

FTIR: propene: 34% by weight

Ethene: 61% by weight

EΝB: 5% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 1.78 dl / g

DSC: (2nd heating) glass transition temperature: T _g = -48 ° C

Enthalpy of fusion: H _m = 42 J / g

Melting peak: T _ml = + 6 ° C ^ = + 75 ^ Example 49

Ethene propene ethylidenenorbornene terpolymerization

100 ml of dry n-hexane distilled under inert gas, 10 g of propene and 2 g of 5-ethylidene-2-norbornene were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At an internal temperature of 50 ° C, the pressure was increased from 4 bar with ethene to 6.5 bar. 2.5x10 ^"7 mol [(flu) Et ₂ PB (C ₆ F ₅ ) ₂ (cp) ZrCl ₂ ] (compound no. 31) and 1.65 ml of a 10% toluene MAO solution (2nd , 5 mmol) The catalyst was added via a pressure lock and the pressure was increased from 6.5 bar to 9 bar The polymerization ran in the temperature range 50 ° -55 ° C. and was terminated after 30 minutes. Hydrochloric acid 90/10 stirred, filtered, washed with ethanol and dried to constant weight in a vacuum drying cabinet at 80 ° C.

Polymer yield: 7.5 g catalyst activity: 60.0 tons of EP rubber per mol Zr and hour

FTIR: propene: 39% by weight

Ethene: 53% by weight

ENB: 8% by weight

Intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 2.32 dl / g

GPC: (universal calibration using M _w = 239 kg / mol of polystyrene standards) M _n = 107 kg / mol

DSC: (2nd heating) Glass transition temperature: T _g = -47 ° C

Enthalpy of fusion: H _m = 10 J / g

Melting peak: T _m = -10 ° C Comparative Example 1 (propene polymerization)

Approx. 1 mol of propene was placed in a dry, oxygen-free 300 ml V4A steel autoclave and the bulk polymerization was started at 20 ° C. by adding a catalyst using a pressure lock. As the catalyst, l lO served ^_6 Mol

[(Me ₃ Si-cp) Ph ₂ PBCl2 (Cp) ZrCl2] and 1 x 10 " ² mol MAO in 9 ml toluene.

The internal temperature rose from 20 ° to 24 ° C. After one hour, 3.2 g of a rubber-like polypropylene could be isolated after working up with ethanol / hydrochloric acid and drying.

Catalyst activity: 3.2 tons per mol-h

DSC: amorphous PP, Tg = -4 ° C

GPC (polystyrene calibration): M _w = 143 kg / mol M _n = 28 kg / mol

Intrinsic viscosity (o-Cl ₂ -benzene, 140 ° C) η = 0.66 dl / g

NMR (triad analysis) 37% isotactic

42% atactic 21% syndiotactic

Here the significantly lower molecular weight and catalyst activity become clear.

Comparative Example 2 (Ethene-propene copolymerization)

100 ml of dry toluene and 10 g of propene distilled under inert gas were placed in a dry, oxygen-free 300 ml V4A steel autoclave. At 20 ° C, the catalyst was added under pressure using a pressure lock and the internal pressure was immediately increased from 2.5 bar with ethene to 6.5 bar. The inside temperature rose to 28 ° C. A mixture of 5 × 10 ⁷ mol [(Me ₃ Si-cp) Ph ₂ PBCl2 (cp) ZrCl2] and preformed at room temperature for about 10 minutes served as the catalyst

5 x L0 ³ moles of methylalumoxane (MAO) in 4.1 mL of toluene. The polymerization was stopped after 30 minutes.

Polymer yield: 5.2 g catalyst activity: 20.8 tons of EP rubber per mole

Catalyst and hour intrinsic viscosity in ortho-dichlorobenzene at 140 ° C: [η] = 1.51 dl / g GPC in ortho-dichlorobenzene at 140 ° C: M _w = 309 kg / mol, M _n = 106 kg / mol IR: 46% by weight propene, 54% by weight ethene DSC: amorphous copolymer with Tg = -55 ° C

In view of the low polymerization temperature, an insufficient molar mass can be observed, which will become significantly worse at higher polymerization temperatures.

Comparative Example 3 (Ethene-propene-ethylidene norbornene terpolymerization)

The procedure was as in comparative example 2, as a catalyst, but 5 x L0 ⁷ mol rac served -. [(Ind) Et ₂ PbCl ₂ (ind) ZrCl _2] activated with 5 x 10 ^"3 moles of MAO The internal pressure was charged with ethene to The polymerization took place in the presence of 1 g of ethylidene-norbornene (ENB) The terpolymer formed (1.5 g) contained 63% by weight of ethene, 35% by weight of propene, 2% by weight of ENB The intrinsic viscosity in ortho-dichlorobenzene at 140 ° C. was 1.86 dl / g. The GPC measurement in o-Cl ₂ -benzene at 140 ° C. gave M _w = 460 kg / mol, M _n = 203 kg / mol The DSC measurement in the second heating showed an amorphous polymer with a glass transition Tg = -50 ° C.

In view of the low polymerization temperature, an insufficient molar mass can be observed, which will become significantly worse at higher polymerization temperatures. Comparative Example 4 (Ethene-Propen-ENB-Terpolvmerisatiori)

The procedure was as in the previous example, but the amount of MAO was only 1 × 10 ^-3 mol and the polymerization temperature was 40 to 45 ° C. The catalyst activity was 4.4 tons of EPDM per mole of catalyst per hour. The intrinsic viscosity (o-

Cl ₂ -benzene, 140 ° C) was 1.34 dl / g. The glass level was at Tg = -52 ° C.

The low activity and molecular weight become clear.

Comparative Example 5 (Ethene-Propene-ENB Terpolymerization)

The procedure was as in the previous example, but the polymerization was carried out at 40 to 46 ° C. in the presence of 2 g of ENB and with 5 × 10 " ³ moles of MAO. The catalyst activity was 11.2 tons of EPDM rubber per mole of catalyst per hour η value (o-Cl ₂ -benzene, 140 ° C) = 1.50 dl / g.M _w = 302 kg / mol, M _n = 112 kg / mol.

The copolymer composition was:

69% by weight of ethene, 28% by weight of propene, 3% by weight of ENB.

The glass level was Tg = -42 ° C.

Low activity combined with insufficient ENB installation.

Claims

Patentansprtiche

1. transition metal compounds with at least two π systems and at least one donor-acceptor interaction between the π systems, characterized in that these transition metal compounds have at least one fluorine-substituted aryl group on at least one acceptor atom.

2. transition metal compounds according to claim 1, characterized in that the acceptor group contains as an acceptor atom an element from the 13th group of the Periodic Table of the Elements according to IUPAC 1985.

3. transition metal compounds according to claim 1 or 2, characterized in that all substituents on the acceptor atom are fluorine-substituted aryl groups.

4. transition metal compounds according to any one of claims 1 to 3, characterized in that the fluorine-substituted aryl group is perfluorinated.

5. transition metal compounds according to any one of claims 1 to 4, characterized in that the fluorine-substituted aryl group is a perfluorophenyl substituent.

6. transition metal compounds according to claim 1, wherein the π systems are cyclopentadienyl, indenyl and / or fluorenyl ligands.

7. Use of the transition metal compounds according to one of claims 1 to 6 as catalysts.

8. Reaction products of cocatalysts with transition metal compounds according to one of claims 1 to 6.

, Process for homo- or copolymerization of one or more olefins, i-olefins, alkynes or diolefins as monomers or for ring-opening polyaddition in the gas, solution, bulk, high pressure or slurry phase at -60 to +250 ° C, characterized in that the polymerization is carried out in the presence of at least one transition metal compound according to one of claims 1 to 6 or a reaction product according to claim 8.

10. The method according to claim 9, characterized in that the method is carried out in the presence of one or more cocatalysts.

11. The method according to any one of claims 9 to 10, characterized in that the transition metal compounds and / or the cocatalysts are applied to a support before the polymerization and then used in supported form.

12. Use of the transition metal compounds according to one of claims 1 to 6 or claim 8 as catalyst components for the production of ultra-high molecular weight polyethylene with M _w > 10 ⁶ g / mol.

13. Use of the transition metal compounds according to one of claims 1 to 6 and claim 8 as catalyst components for the production of - high molecular weight EP (D) M with M _w > 10 ⁵ g / mol.

14. Use of the transition metal compounds according to one of the claims

1 to 6 and claim 8 as catalyst components for the production of ultra-high molecular weight EP (D) M with M _w 10 ⁶ g / mol.

15. Use of the transition metal compounds according to one of claims 1 to 6 and claim 8 as catalyst components for the production of high molecular weight polypropylene with M _w > 10 ⁵ g / mol.

16. Use of the transition metal compounds according to one of claims 1 to 6 and claim 8 as catalyst components for the production of ultra-high molecular weight polypropylene with M _w > 10 ⁶ g / mol.

17. Use of the transition metal compounds according to one of claims 1 to 6 and claim 8 as catalyst components for the production of atactic high molecular weight polypropylene with M _w > 10 ⁵ g / mol.

18. Use of the transition metal compounds according to one of the claims

1 to 6 and claim 8 as catalyst components for the production of long-chain branched polymers.