CA2084016C - Process for the preparation of substituted indenes and their use as ligand systems for metallocene catalysts - Google Patents

Abstract

The invention relates to a process for the preparation of a compound of the formula IV or IVa (see formula IV and IVa) in which R1-R5 are preferably hydrogen or alkyl, which comprises reacting a compound I

(see formula I) with a compound II

(see formula II) in which X1 and X2 are preferably halogen, to give the corresponding indanones, which are converted into the compounds IV and IVa by reduction and dehydra-tion. The compounds IV and IVa are important intermediate products for the preparation of chiral metallocene complexes which are suitable catalyst components for olefin polymerization.

Description

HOECHST AKTTENGESELLSCHAFT HOE 91/F 375 Dr.LO/AL
Description Process for the preparation of substituted indenes and their use as ligand systems for metallocene catalysts The present invention relates to a simple process for the preparation of indene derivatives substituted on the five- and six-membered rings.
Compounds of this type are important intermediate pro-ducts in the preparation of metallocene complexes. In particular, the corresponding bridged, chiral zirconium derivatives are of great importance as highly active catalysts in olefin polymerization (cf. EP-A 129 368).
The properties of the catalysts can be influenced in a controlled manner by varying the ligand system, for example by substitution. It is thereby possible to modify the polymer yield, the molecular weight, the tacticity or the melting point of the polymers to the desired extent (Flew J. Chem. 14 (1990) 499; Organomet. 9 (1990) 3098;
Angew. Chem. 102 (1990) 339; EP-A 316 155; and EP-A 351 392).
Indenes furthermore can also be employed as monomers in homopolymerization or copolymerization with other olefins (cf. Macromol. 22 (1989) 3824; and Bull. Soc. Chim. Fr.
6 (1969) 2039).
However, the few substituted indenes described in the literature as a rule are accessible only in low yields via multi-stage syntheses. They are usually obtained from the correspondingly substituted 1-indanones by reduction and subsequent dehydration. The corresponding indanones are obtainable in multi-stage syntheses starting from substituted aromatics (Bull. Soc. Chim. Fr. 6 (1969) 1981; Acta Chem. Scand. B 30 (1976) 527; Austr. J. Chem.
29 (1970) 2572; Chem. Lett. (1981) 729; and Ber. 97(12) (1964) 3461).

_ 2 _ Certain substitution patterns moreover are not accessible by this route.
There was the task of discovering a process for the preparation of the abovementioned indenes which avoids the disadvantages known from the prior art. Such indenes allow access to novel metallocene complexes.
It has been found that aromatics of the following formula I react with derivatives of p:ropionic acid carrying a leaving group in the a-position and with a Friedel-Crafts catalyst to give substituted 1-indanones in high yields.
This result was completely unexpected, since these products would have been expected only with derivatives of propionic acid which carry a leaving group in the p-position (cf. J. Amer. Chem. Soc. 72 (1950) 3286).
Moreover, this synthesis is a one-stage process which is easy to handle industrially. The indanones can then be converted into the corresponding indenes by known methods. At the same time, the process according to the invention allows the preparation of novel compounds of the structure type mentioned.
The present invention therefore relates to a process for the preparation of a compound of the formula IV or an isomer thereof of formula IVa R Ri Rs (IV) ~ ~ s (IVa) R~ Ro in which R', RZ, R3, R° and R5 are identical or different and are hydrogen, ( Cl-CZO ) alkyl , ( C6-C~4 ) aryl , ( C1-Clo ) alkoxy, ( CZ-Clo ) alkenyl , ( C~-Czo ) arylalkyl , ( C~-CZO ) alkyl aryl, ( C6-Clo ) aryloxy, ( C1-Clo ) -f luoroalkyl , ( C6-Clo ) halogenoaryl, ( CZ-Clo ) alkynyl , a radical -~iR63, in which Rs is ( Cl-C1o ) -alkyl, a halogen atom or a heteroaromatic radical which has 5 or S ring members and can contain one or more hetero atoms, or adjacent radicals R1-R4, with the atoms joining them, form one or more rings, which comprises reacting a compound of the formula I
Rt O (I) with a compound of the formula II

(II) ~ \X2 or an anhydride thereof, in the presence of a Friedel-Crafts catalyst to give a compound of the formula ITI or of the formula IIIa R~
R~ 0 R

Rs O ~ RS
R3 (III) Rl (IIIa) Re 0 R' in which R1-RS have the meanings given and X1 and X2 are identical or different and are a nucleophilic leaving group, and converting this into the compound of the formula IV or IVa by reduction and dehydration by known methods.

.~

Tn these formulae, alkyl is straight-chain or branched alkyl. Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine. Examples of hetero-aromatic radicals are thienyl, furyl or pyridyl.
~'he indanones can be obtained in the form of two struc-tural isomers of the formula III and IIIa, depending on the substitution pattern on the aromatic radical. These isomers can be reduced, in the pure form or as a mixture, with reducing agents such as AfaBH4 or LiAlH,, by methods which are known from the literature, to give the corres-ponding indanols, which can then be dehydrated with acids, such as sulfuric acid, oxalic acid or p-toluene-sulfonic acid, or by treatment with dehydrating sub-stances, such as magnesium sulfate, sodium sulfate, aluminum oxide, silica gel or molecular sieves, to give indenes of the formula IV or IVa (Bull. Soc. Chim. Fr. 11 (1973) 3092; Organomet. 9 (1990) 3098 and the embodiment examples).
X1 and Xz are preferably a halogen atom, a hydroxyl group, a tosyl group or a (Cz-Clo)alkoxy group; in particular a halogen atom, particularly preferably bromine or chlorine.
Suitable Friedel-Crafts catalysts are, for example, A1C13, AlBr3, FeCl3, SbClS, SnCl4, BF3, TiCl,,, ZnCl2, HF, HZS04, polyphosphoric acid, H3P04 or an A1C13/NaCl melt; in particular A1C13.
In the formulae IV and IVa, preferably, R1, R2, R3 and R4 are identical or different and are hydrogen, ( Cl-C1o ) alkyl, ( C6-C1,, ) aryl, ( C1-C4 ) alkoxy, (CZ-C6)alkenyl, (Cl-C6)fluoroalkyl, a halogen atom or a heteroaromatic radical which has 5 or S ring members and can contain one or more hetero atoms, or adjacent radicals Rl-R4, with the atoms joining them, form a ring, and R5 is ( C1-Cto ) alkyl .
Tn particular, R1, RZ, R3 and R4 are identical or different and are hydrogen or ( C1-Clo ) alkyl, or the radicals Rl and RZ or R3 and R4, with the atoms joining them, form a ring, and RS
is methyl.
The starting compounds of the foxmulae I and II are known and are commercially obtainable, or they can be prepared by processes which are known from the literature.
The reaction is carried out in an inert solvent.
Methylene chloride or CFZ is preferably employed. If the starting components are liquid, a solvent can also be dispensed with.
The molar ratios of the starting compounds, including the Friedel-Crafts catalyst, can vary within wide limits. The molar ratio of compound I:II:catalyst is preferably 1:0.5-1.5:1.5; in particular 1:1x2.5-3.
The reaction temperature is preferably 0°C to 130°C, in particular 25°C to 80°C.
The reaction times as a rule vary between 30 minutes and 100 hours, preferably between 2 hours and 30 hours.
Rreferably, a mixture of compounds I and II is initially introduced into the reaction vessel and the Friedel Crafts catalyst is metered in. The reverse sequence of addition is also possible.
The indanones of the formula III or IIIa can be purified by distillation, column chromatography or by crystalliz-ation.

The substituted indenes can be obtained as double bond isomers (IV/IVa). These can be purified from by-products by distillation, column chromatography or crystallization.
The process according to the invention is distinguished in partcular in that variously substituted indenes can be obtained in a high yield in a simple and short synthesis.
The substitution pattern on the five- and six-membered ring can be varied within a very wide range in this process. This means that novel indene derivatives are also accessible.
The present invention furthermore relates to the use of the indene derivatives IV/IVa as an intermediate product in the preparation of metallocene complexes, in parti cular of those of the following formula VI.
The metallocenes of the formula VI are novel and the present invention likewise relates to them.

RS O

R' 1Q (VI) R R ~W R11 O ~ RS
R2 ~ r in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1, Rz, R3, R4 and RS are identical or different and are hydrogen, ( Gl-Czo ) alkyl, ( C6-C14 ) aryl, ( C1-Clo ) alkoxy, ( Cz-Clo ) alkenyl, ( C~-Czo ) arylalkyl, ( C~-Czo ) alkylaryl, ( Co-Clo ) aryloxy, ( C1-Clo ) fluoroalkyl, ( C6-Clo ) halogenoaryl, ( Cz-Clo ) alkynyl, a radical -SiR63, in which R6 is ( Cl-C1o ) -alkyl, a halogen atom or a heteroaromatic radical which ~~t~~~.~~
has 5 or 6 ring members and can contain one or more hetero atoms, or adjacent radicals R1-R4, with the atoms joining them, form one or more rings, Rs R' is a radical I , ~z Re P
in which MZ is carbon, silicon, germanium or tin, Rs and R9 are identical or different and are hydrogen, ( Ci-Czo ) alkyl, ( Cs-Cla ) aryl ~ ( Ci-Cio ) alkoxyo ( Cz-Cio ) alkenyl, ( CwCao ) arylalkyl , ( C~-Czo ) alkyl aryl, ( Cs-Coo ) aryloxy, ( Ci-Cl° ) f luoroalkyl, ( Cs-C1° ) halogenoaryl, ( CZ-C1° ) alkynyl or halogen, or R8 and R9, together with the atom joining them, form a ring, p is 0, 1, 2 or 3 and R1° and R11 axe identical or different and are hydrogen, ( C1-Coo ) alkyl, ( C1-Clo ) alkoxy. ( Cs-Cio ) aryl ~ ( Cs°C~o ) ar'Yloxyo ( CZ-C1° ) alkenyl, ( C~-C4o ) arylalkyl, ( C~-C4° ) alkylaryl, (C8-C4o)arylalkenyl, hydroxyl or a halogen atom.
Preferably, M1 is zirconium or hafnium, in particular zirconium, R1, Rz, R3 and R4 are identical or different and are hydrogen, ( Cl-Clo ) alkyl , ( Cs-C14 ) aryl, ( C1-C4 ) alkoxy, (CZ-Cs)alkenyl, (Cl-Cs)fluoroalkyl, a halogen atom or a heteroaromatic radical which has 5 or 6 ring members and can contain o:ne or more hetero atoms, and RS is (C1-Clo)-alkyl, or adjacent radicals R1-R'', with 'the atoms joining them, form a :ring, MZ is carbon or silicon, in particular silicon, R8 and R9 are identical or different and are hydrogen, (C1-Cs)alkyl, _8-( Cs-C1° ) aryl , ( C1-Cs ) alkoxy, ( CZ-C,, ) alkenyl, ( C~-C1° ) arylalkyl or ( C~-C1° ) alkyl aryl , or RB and R9, together with the atom joining them, form a ring, p is 1 or 2, preferably 1, and Rl° and Rll are identical or different and are hydrogen, (Cs-C3)alkyl, in particular methyl, (C1-C3 ) alkoxy, ( Cs-Cs) aryl, ( Cs-C8 ) aryloxy, ( C2-C4 ) alkenyl, ( C~-Cl° ) arylalkyl, ( C~-C1° ) alkylaryl, ( CB-C12 ) arylalkenyl or a halogen atom, preferably chlorine.
Preferably, the radicals R1° and R11 axe identical and are chlorine or methyl. M2 is, in particular, silicon, and the radicals R8 and R9 are identical or different and are preferably (C1-Cs)alkyl, preferably methyl, or (Cs-Clo)-aryl.
Furthermore, for the compounds of the formula VI, RS arid R3; R1, R3 and R5; R1, R2, R3 and RS or all the radicals R1-RS are preferably other than hydrogen and are preferably (C1-C4)alkyl. Particularly preferably, the radicals R', R3 and R5 are other than hydrogen, are identical or different and are ( Cl-C4 ) alkyl .
The preferred substitution patterns on the indenyl radicals are therefore 2,6-, 2,4,6-, 2,4,5-, 2,4,5,6- and 2,4,5,6,7-, in particular 2,4,6- and 2,4,5-. The 2-position here on the indenyl radicals (RS) is preferably substituted by a methyl group. Furthermore, for the compounds of the formula VI, the indenyl radicals are benzo-fused.
The compounds VI mentioned in the embodiment examples are of particular importance.
Starting from the indenes of the formulae IV and IVa, which can be employed as an isomer mixture, the prepara-tion of the metallocenes VI proceeds by processes which are known from the literature (cf. AU-A-31478/89, J.
c~rganomet. Chem. 342 (1988) 21, EP-A 284 707 and the ~~9~~~~~' embodiment examples) in accordance with 'the following equation:
Rf R~

R3 ~ ~
2 IV~IVO °) 2 Bulylli R R~ (y) Rf D) X3-R)-X3 ~
R

R~
Rf RS O
Y ~R 3 a) 2 Bufylli R°
(VI) - - -+ R~ R2 t b ) 0.1 f C I 4 3 w C I Z
R
O ~R 5 R
R~
(X3 = a nucleophilic leaving group, such as, for example, C1, Br or 0-tosyl).
The metallocene halides of the formula VT can be deriva tized by methods which are known from the literature, for example by reactions with alkylating agents, such as lithiumalkyls, to give the corresponding mono- or dialkyl compounds (J. Amer. Chem. Soc. 95 (1973) 6263).
The bridged ligand systems of the formula V can be obtained as structural isomers, depending on the substi-tution pattern of the indene. If these isomers are not separated, structural isomers of metallocenes of the formula VI are formed. The metallocenes of the formula VI
are obtained as a mixture of the racemic form with the ..
- to -meso form. The separation of the isomeric forms, in particular the removal of the mesa form, which is undesirable for the olefin polymerization, is known in principle (AU-A-31478/89; J. Organomet. Chem. 342 (1988) 21; and EP-A 284 707 ) . It is as a rule carried out by extraction or recrystallization using various solvents.
The present invention furthermare relates to the use of the compounds of the formula VI as catalyst components in olefin polymerization.
The metallocenes VI are highly active catalysts and are suitable, for example, for the preparation of olefin polymers of high isotacticity and high molecular weight.
The polymerization or copolymerization is carried out in a known manner in solution, in suspension or in tkie gas phase, continuously or discontinuously, in one or more stages, at a temperature of 0 to 150°C, preferably 30 to 80°C. Olefins of the formula Ra-CH=CH-Rb are polymerized or copolymerized. In this formula, Re and Rb are identical or different and are a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms. However, Ra and Rb, with the carbon atoms joining them, can also form a ring. Examples of such olefins are ethylene, propylene, 1-butane, 1-hexane, 4-methyl-1-pentane, 1-octane, norbornene, dimethaneoctahydronaphthalene or norbornadiene. In particular, propylene and ethylene are polymerized (cf., for example, EP-A 129 368).
Aluminoxanes are preferably used as cocatalysts (cf.
EP-A 129 368; Polyhedron 9 (1990) 429 and the embodiment examples).
According to the invention, instead of or in addition to an aluminoxane, compounds of the formulae R,~NH,,_RBR'4, R,~PH4_XBR' 4, R3C:BR' 4 or BR' 3 can be used as suitable co-catalysts. In these formulae, x is a number from 1 to 4, ~~~~~:~.

preferably 3, the radicals R are identical or different, preferably identical, and are C1-Clo-alkyl or C6-C18-aryl, or two radicals R, together with the atom joining them, form a ring, and the radicals R' are identical or dif-ferent, preferably identical, and are C6-C18-aryl, which can be substituted by alkyl, haloalkyl or fluorine (EP-A 277 003, 277 004, 426 638 and 427 697).
The following examples serve to illustrate the invention in more detail.
Example A
2,5,7-Trimethyl-1-indanone (1) 107 g (810 mmol) of A1C13 are slowly added to a solution of 34.4 g (324 mmol) of m-xylene (99~ pure) and ?4 g (324 mmol) of 2-bromoisobutyryl bromide (9$~ pure) in 600 ml of analytical grade methylene chloride via a solids metering funnel at room temperature, while stir-ring vigorously, whereupon vigorous evolution of gas started. The mixture was stirred at room temperature for 15 hours, poured onto ice-water, which was acidified with 25 ml of concentrated HC1, and extracted several times with ether. The combined organic phases were washed first with a saturated NaHC03 solution and then with a saturated NaCl solution and dried with magnesium sulfate. The ail which remained after the solvent had been stripped off under reduced pressure was distilled over a short distillation bridge. 52.4 g of the indanone 1 passed over at 81-90°C/0.1-0.2 mbar in the form of a colorless oil which crystallized at room temperature. The yield was 93$.
1H-NMR spectrum (100 MHz, CDC13): 7.05 (1,s), 6.87 (l, s), 3.25 (1,g), 2.43-2.80 (2,m), 2.57 (3,s), 2.35 (3,s), 1.25 (3,d).
Mass spectrum: 174 M+, correct disintegration pattern.

Example B
2,4,6-Trimethylindene (2) 20.4 g (117 mmol) of 2,5,7-trimethyl-1-indanone (1) were dissolved in 300 ml of a mixture of tetrahydrofuran/-methanol (2:1), and 6.6 g (175 mmol) of NaBH4 were added at room temperature. The mixture was stirred for a further hour, 50 ml of half-concentrated HCl were added and the mixture was extracted with ether. The combined organic phases were dried over sodium sulfate and freed from the solvent. The residue was transferred to a distillation apparatus, and 13 g of magnesium sulfate were added. A vacuum of about 10 mbar was applied and the mixture was heated up until the product distilled over (130-150°C). Distillation gave 17.? g of the indene 2 as a colorless oil. The yield was 96~.
1H-NMR spectrum (100 MHz, CDC13): double bond isomers A:B = 2:1 Isomer A: 6.97 (1,s), 6.80 (l, s), 6.50 (1,m), 3.20 (2,m), 2.1-2.3 (9,m).
Isomer B: 6.87 (l, s), 6.70 (l, s), 6.37 (l, m), 3.07 (2,m), 2.1-2.3 (9,m).
Mass spectrum: 158 M~, correct disintegration pattern.
Example C
2-Methyl-5,7-diisopropyl-1-in_danone (3) and 2-methyl-4,6-diisopropyl-1-indanone (3a) 174 g (1300 mmolj of A1C13 were slowly added to a solution of 84.8 g (523 mmol) of 1,3-diisopropylbenzene and 120 g (523 mmol) of 2-bromoisobutyryl bromide (98~ pure) in 600 ml of analytical grade methylene chloride via a solids metering funnel at room temperature. The mixture was, heated under reflux for a further 20 hours and then worked up analogously to Example A. The crude product was chromatographed on 3 kg of silica gel 60. The indanones 3 and 3a were able to be eluted separately with a mobile phase mixture of hexane/15$ ethyl acetate. Using the same mobile phase, the compound 2-methyl-5-isopropyl-I-indanone followed as a by-product in a further zone.
However, separation of the two isomers is not necessary for the further reactions . The overall yield was 93 g (78~).
1H-NMR spectrum (360 MHz, CDC13): isomer mixture (3:2) 7.49 (d), 7.36 (d), 7.13 (s), 7.10 (s), 4.15 (septet), IO 3.25--3.40 (m), 3.10 (septet), 2.90-3.00 (m), 2.60-2.73 (m), 1.22-1.30 (m).
Mass spectrum: 230 M+, correct disintegration pattern.
Example D
2-Methyl-4,6-diisopropylindene (4) and 2-methyl-5,7-diisopropylindene (4a), variant I
19 . 3 g ( 511 mmol ) of NaBH4 were added to a solution of 78.5 g (341 mmol) of the isomer mixture 3/3a in 700 ml of a solvent mixture of tetrahydrofuran/analytical grade methanol (2:1) at room temperature. After the mixture had been stirred at room temperature for 2 hours, 120-130 ml of half-concentrated HC1 were added and the mixture was extracted with ether. The combined organic phases were dried with NazSO,,. The residue which remained after the solvent had been stripped off was taken up in 500 ml of methylene chloride, and the mixture was heated under reflux with 6.5 g (34 mmol) of p-toluenesulfonic acid for 15 minutes. The residue which remained after the solvent had been stripped off was chromatographed on 1.5 kg o~
silica gel 60. Using a mobile phase mixture of hexane/di-isopropyl ether 20 s 1, 56 g of the isomer mixture 4/4a were able to be isolated in the form of a colorless oil.
The overall yield was 86$.
1H-NMR spectrum (100 MHz, CDC13): double bond isomers (1:1) 7.1 (m), 6.95 (m), 6.60 (m), 6.43 (m), 3.25 (br), 2.75-3.20 (m), 2.12 (d), 1.28 (d), 1.25 (d).

~~~~:~~~E

Mass spectrum: 214 M+, correct disintegration pattern.
Example E
2-Methyl-4,6-diisopropylindene (4) and 2-methyl-5,7-diisopropylindene (4a), variant II
19 . 3 g ( 511 mmol ) of NaBH4 were added to a solution of 78.5 g (341 mmol) of the isomer mixture 3/3a in 700 ml of a solvent mixture of tetrahydrofuran/analytical grade methanol (2:1). After the mixture had been stirred at room temperature for 2 hours, 120-130 ml of half-concentrated HCl were added and the mixture was extracted with ether. The combined organic phases were dried with Na2S04. The residue which remained after the solvent had been stripped off was transferred to a distillation apparatus, and 50 mg of magnesium sulfate were added.
After a vacuum of about 1 mbar had been applied, the mixture was heated up until the product passed over (about 130°C). 65 g of the isomer mixture 4/4a were obtained as a colorless oil. The yield was 90~.
Example F
2-Methyl-1-indanone (5) 17 . 3 g ( 125 mmol ) of A1C13 were added to a solution of 3.91 g {50 mmol) of benzene in 30 ml of analytical grade methylene chloride, while cooling with ice. 11.9 g (52 mmol) of 2-bromoisobutyryl bromide were then added, and stirring was continued at 0°C for 1 hour and at room temperature for 2 hours. The mixture was heated under reflux for a further 15 hours and then worked up analo gously to Example A. The crude product was chromato graphed on 100 g of silica gel (hexane/methylene chloride 1:1). The yield was 5.1 g (70~).
1H-NMR spectrLUn ( 100 MHz, CDC13) : 7 . 5 (m) , 3. 33 {q) , 2 . 73 (m), 1.30 (d).

Mass spectrum: 146 M+, correct disintegration pattern.
Example G
2-Methylindene (6) Analogously to Example D, 5.0 g (34 mmol) of 2-methyl-1-indanone (5) were reduced with 1..94 g (52 mmol) of NaBH4.
The alcohol, which was not purified further, was then further reacted in the presence of 0.2 g of p-toluene sulfonic acid in 100 ml of toluene at 80°C. Chromato graphy on 100 g of silica gel (hexane/methylene chloride 9:1) gave 3.68 g (82~) of 2-methylindene (6).
1H-NMR spectrum (100 MHz, CDC13): 7.2 (4,m), 6.45 (l, m), 3.25 (2,m), 2.1 (3,m).
Mass spectrum: 130 M+, correct disintegration pattern.
Example H
2-Methyl-5-isobutyl-1-indanone (7) 17 . 3 g ( 125 mmol ) of A1C13 were added to a solution of 6 . 71 g ( 50 mmol ) of isobutylbenzene in 30 ml of analy-tical grade methylene chloride, while cooling with ice.
11.9 g (52 mmol) of 2-bromoisobutyryl bromide were then added rapidly, and stirring was continued at 0°C for 1 hour and at room temperature for 2 hours. The mixture was heated under reflux for a further 15 hours and then worked up analogously to Example A. The crude product was chromatographed on 100 g of silica gel (hexane/methylene chloride 1:1). The yield was 8.42 g (83~).
1H-NMR spectrum (100 MHz, CDC13): 7.7 (m), 7.2 (m), 3.35 (q), 2.70 (m), 2.58 (d), 1.95 (q), 1.25 (d), 0.93 (d).
Mass spectrum: 202 M+, correct disintegration pattern.

Example J
2-Methyl-6-isobutylindene (8) Analogously to Example D, 8.3 g (41 mmol) of 2-methyl-5-isobutyl-1-indanone (7) were reduced with 2.4 g (62 mmol) of NaBH4. The alcohol, which was not purified further, was then further reacted in the presence of 0.4 g of p-toluenesulfonic acid in 100 ml of toluene at 80°C.
Chromatography on 400 g of silica gel (hexane) gave 7.17 g (95~) of 2-methyl-6-insobutylindene (8).
1H-NMR spectrum (100 MHz, CDC13): 7.1 (m), 6.45 (m), 3.25 (m), 2.45 (d), 2.88 (q), 2.10 (d), 0.95 (d).
Mass spectrum: 184 M+, correct disintegration pattern.
Example K
2,5,6,7-Tetramethyl-1-indanone (9) 17 . 3 g ( 125 mmol ) of A1C13 were added to a solution of 6 . O1 g ( 50 mmol ) of 1, 2, 3-trimethylbenzene in 30 ml of analytical grade methylene chloride, while cooling with ice. 11.9 g (52 mmol) of 2-bromoisobutyryl bromide were then added rapidly, and stirring was continued at 0°C for 1 hour and at room temperature for 2 hours. The mixture was kept at room temperature for a further 15 hours and then worked up analogously to Example A. The crude product was purified by distillation (0.05 mm Hg/96-107°C). The yield was 8.1 g (86~).
1H-NMR spectrum (100 MHz, CDC13): 7.0 (m), 3.20 (q), 2.60 (rn), 2.20 (m), 1.25 (d).
Mass spectrum: 188 M+, correct disintegration pattern"

~ ~ ~ !~ ~ ~~. E' _ 17 _ Example L
2,4,5,6-Tetramethylindene (10) Analogously to Example D, 1.50 g (8 mmol) of 2,5,6,7-tetramethyl-1-indanone (9) were reduced with 0.45 g (12 mmol) of NaBH4. The alcohol, which was not purified further, was then further reacted in the presence of 0.1 g of p-toluenesulfonic acid in 100 ml of toluene.
Chromatography on 100 g of silica gel (hexane/methylene chloride 9:I) gave 0.88 g (65~) of 2,4,5,6-tetramethyl IO indene (10).
1H-NMR spectrum (I00 MHz, CDC13): 7.0 (s), 6.45 (m), 3.25 (m), 2.60 (m), 2.20 (m), 2.10 (d). Mass spectrums 170 M+, correct disintegration pattern.
Example M
Dimethylbis(2-methyl-4,6-diisopropylindenyl)silane (II) 9 . 2 ml ( 22 . 8 mmol ) of a 2 . 5 M butyllithium solution in hexane were added to a solution of 4.9 g (22.8 mmol) of the isomer mixture 4/4a in 25 ml of tetrahydrofuran at 0°C under Ar as an inert gas, and the mixture was heated under reflux for a further hour. The red solution was then added dropwise to a solution of I.5 g (11.4 ml) of dimethyldichlorosilane in IO ml of tetrahydrofuran, and the mixture was heated under reflux for 8 hours. The batch was poured onto ice-water and extracted with ether.
The ether phase was dried over magnesium sulfate and evaporated under reduced pressure. The yellowish oil which remained was then chromatographed on 500 g of silica gel 60. With a mobile phase mixture of hexanel5~
methylene chloride, 1.4 g of the indene mixture 4/4a were able to be eluted first. The ligand system I1 followed with hexane/8~ methylene chloride. The viscous oil which remained after the mobile phase had been stripped off was able to be crystallized by stirring with methanol in an - is -ice bath. 3.1 g of a yellowish solid were obtained. The yield was 56~, or 84~ with respect to the indene reacted.
1H-NMR spectrum (100 MHz, CDC13): double bond isomers (3:1) 6.82-7.32 (m), 6.70 (m), 6.62 (m), 6.52 (m), 3.75 (s,br), 3.65 (s,br), 3.35 (s), 2.70-3.30 (m), 2.05-2.25 (m), 1.10-1.45 (m), 0.10-0.22 (m), -0.15 to -0.32 (m).
Mass spectrum: 484 M~, correct disintegration.
Example N
Dimethylsilanediylbis(2-methyl--4,6-diisopropylindenyl)-zirconium dichloride (12) 6 . 3 ml ( 16 . 2 mmol ) of a 2 . 5 M butyllithium solution in hexane were added to a solution of 3 . 1 g ( 6 . 5 mmol ) of the ligand system 11 in 25 ml of diethyl ether at room temperature under Ar as the inert gas, and the mixture was stirred overnight. After addition of 10 ml of hexane, the beige-colored suspension was filtered and the residue was washed with 20 ml of hexane. The dilithium salt was dried under an oil-pump vacuum for a long time and then added to a suspension of 1. 6 g ( 6 . 8 mmol ) of ZrCl4 in 30 ml of methylene chloride at -78°C. The mixture was warmed to room temperature in the course of 1 hour and stirred at this .temperature for a further 30 minutes.
After the solvent had been stripped off, the orange-brown residue was extracted with 50 ml of hexane. After the solvent had been stripped off, 2.6 g (60~) of the complex 12 were obtained in the form of a yellow powder. The ratio of the racemate to the meso form was 3:1. 1.3 g (30$) of the complex 12 were able to be obtained as the pure racemate by recrystallization from hexane (yellow crystalline powder).
1H-NMR spectrum (100 MHz, CDC13): 7.27 (2,s,aromatic-H), 7.05 (2,s,aromatic-H), 6.80 (2,s,~9-Ind-H), 2.6-3.2 (4,m,i-Pr-CH), 2.22 (6,s,Ind-CH3), 1.15-1.40 (30,m, i-Pr-CH3, Si-CH3). Mass spectrum: 642 M+ (with respect to s°Zr), correct isotope pattern, correct disintegration.

Example 0 Dimethylbis(2,4,6-trimethylindenyl)silane (13) 25.5 ml (63.7 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 10 .1 g ( 64 mmol ) of the indene 2 in 50 ml of tetrahydrofuran at room tempera-ture under Ar as the inert gas, and the mixture was heated under reflux for 1 hour. The solution thus obtained was added dropwise 1:o a solution of 4.1 g (32 mmol) of dimethyldichlorosilane in 20 ml of tetra-hydrofuran, and the mixture was heated under reflux for 3 hours. The reaction mixture was poured onto ice-water and extracted several times with ether. The combined organic phases were dried over sodium sulfate and evapor-ated under reduced pressure. The residue was chromato-graphed on 450 g of silica gel 60. With a mobile phase mixture of hexane/5~ methylene chloride, 2.5 g of the indene 2 were able to be eluted first. 6.5 g of the ligand system 13 (isomers) followed with hexane/~~
methylene chloride. The yield was 54~, or 72~ with respect to the indene 2 reacted.
Example P
Dimethylsilanediylbis(2,4,6-trimethylindenyl)zirconium dichloride (14) 6 . 6 ml ( 16 . 2 mmol ) of a 2 . 5 I~I butyllithium solution in hexane were added to a solution of 2 . 0 g ( 5 . 4 mmol ) of the ligand system 13 in 30 ml of diethyl ether at room temperature under Ar as the inert gas, and the mixture was stirred at this temperature for 5-6 hours. The solution was evaporated completely. The solid residue which remained was washed in portions with a total of 30 ml of hexane and dried under an oil-pump vacuum for a long time. The beige-colored powder thus obtained was added to a suspension of 1.23 g (5.5 mmol) of zirconium ~~fa~~:~.~

tetrachloride in 30 ml of methylene chloride at -78°C.
After being warmed to room temperature, the reaction mixture was evaporated completely and the residue was dried under an oil-pump vacuum. The solid residue com-prised a mixture of the racemic form with the meso form in a ratio of 1:1. This was first washed with a small amount of hexane. It was then extracted with a total of 120 ml of toluene. The solution was concentrated, and the residue was left to crystallize at -35°C. 800 mg (28~) of the zirconocene Z4 were able to be obtained as the pure racemate in the form of orange-colored Crystals.
1H-NMR spectrum of the racemate ( 100 MHz, CDC13) 7.20 (s,2,aromatic-H), 6.97 (s,2,aromatic-I3), 6.70 (s,2, ~-Ind-H), 2.32 (s,6,CH3), 2.27 (s,6,CH3), 2.20 (s,6,CH3), 1.27 (s,6,Si-CH3).
Mass spectrum: 530 M~ (with respect to 9°Zr), correct isotope pattern, correct disintegration.
Example R
Methylphenylbis(2-methyl-4,6-diisopropylindenyl)silane (15) 18.6 ml (46 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 10 g (46 mmol) of the indene 4/4a in 200 ml of tetrahydrofuran at room tempera-ture under Ar as the inert gas, and the mixture was heated under reflux for I~ hour. The solution was added dropwise to a solution of 4.48 g (23 mmol) of methyl-phenyldichlorosilane in 30 ml of tetrahydrofuran at room temperature, and the mixture was heated under reflux for 3 hours. The mixture was poured onto ice-water and extracted several times with ether. The combined organic phases were dried with sodium sulfate and evaporated. The residue was chromatographed on 450 g of silica gel 60.
With a mobile phase mixture of hexane/methylene chloride (10:1), 1.9 g of unreacted indene 4/4a were able to be recovered first. 7.4 g of the ligand system 15 (isomer ~D~~~~. '~

mixture) then followed. The yield was 57~, or 73~ with respect to the indene reacted.
Example S
Methylphenylsilylbis(2-methyl-.4,6-diisopxopylindenyl)-zirconium dichloride (16) 11.2 ml (28 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 7.4 g (13.5 mmol) of the ligand system 15 in 30 ml of diethyl ether at room temperature under Ar as the inert gas, and the mixture was stirred at room temperature for 16 hours. After the solvent had been stripped off, the residue which remained was dried at 40-50°C for 3-4 hours, and then added to a suspension of 3.2 g (13.5 mmol) of zirconium tetra-chloride in 40 ml of methylene chloride at -78°C. After the mixture had been warmed to room temperature, the solvent was stripped off under reduced pressure. The solid residue which remained was dried under an oil-pump vacuum and extracted with 100 ml of hexane. After the solvent had been stripped off, 5.4 g (55~) of the zircon-ocene 16 were obtained as a mixture of the racemic form with the meso form in a ratio of 2:1 (orange-brown crystalline powder). The pure racemic form is obtainable by recrystallization from hexane.
zH-NMR spectrum of the isomer mixture ( 100 MHz, CDC13) :
6.6-8.2 (m, aromatic-H,~9-Ind-H), 2.5-3.2 (m,i-Pr-H), 2.52 (s,CH3), 2.32 (s,CH3), 2.20 (s,CH3), 1.90 (s,CH3), 1.0-1.5 (m, i-Pr-CH3, Si-CH3 ) .
Mass spectrum: 704 M+ (with respect to 9°Zr), corxect isotope pattern, correct disintegration.

Example T
1,2-Bis(2-methyl-4,6-diisopropylindenyl)ethane (17) 18.6 ml (46 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 5.0 g (23.3 mmol) of the indene 4/4a in 50 ml of tetrahydrofuran at room temperature under Ar as the inert gas, and the mixture was heated under reflux for 1 hour. The solution was added to a solution of 2.18 g (11.0 mmol) of 1,2-dibromo-ethane at -78°C. The solution was warmed slowly to room temperature and stirred at this temperature overnight.
The mixture was poured onto ice-water and extracted several times with ether. The combined organic phases were dried with sodium sulfate and evaporated. The residue was chromatographed on 450 g of silica gel 60.
With a mobile phase mixture of hexane/methylene chloride (20:1 to 10:1), 1.2 g of unreacted indene 4/4a were able to be recovered first. 1.7 g of the ligand system 17 (colorless solid) then followed. The yield was 35~, or 45~ with respect to the indene reacted.
Example U
1,2-Ethanediylbis(2-methyl-4,6-diisopropylindenyl)-zirconium dichloride (1$) 3.5 ml (8.8 moral) of a 2.5 M butyllithium solution in hexane were added to a solution of 1.6 g (3.52 mmol) of the ligand system 17 in 20 ml of diethyl ether at room temperature under Ar as the inert gas, and the mixture was stirred overnight. The residue which remained after the solvent had been stripped off was washed with hexane and dried under an oil-pump vacuum far a long time. The powder thus obtained was added to a suspension of 815 mg (3.5 mmol) of zirconium tetrachloride in 15 ml of methyl-ene chloride at -78°C. After the mixture had been warmed to room temperature, it was stirred for a further hour, and the solvent was removed under reduced pressure. The :residue was dried under an oil-pump vacuum and extracted with toluene. Stripping off the solvent and washing with hexane gave 1.5 g (70~) of the zirconocene 18 as a mixture of the racemic with the meso form in a ratio of 2:1 (orange-colored powder). 700 mg (32~) of the pure racemate were able to be obtaLned by recrystalliza-tion from a toluene/hexane mixture.
1H-NMR spectrum of the racemate (100 MHz, CDC13): 7.3 (s,aromatic-H), 7.0 (s,aromatic~-H), 6.55 (s,~-Ind-H), 3.6 (s,C2H4), 2.6-3.2 (m,i-Pr-H), 2.2 (s,CH3).
Mass spectrum: 612 M+ (with respect to 9°Zr), correct isotope pattern, correct disintegration.
Example V
2-Methyl-6,7-benzoindan-1-one (19a) and 2-methyl-4,5-benzoindan-1-one (19b) 27.5 g (207 mmol) of AlCl3 were added to a solution of 10 g (83 mmol) of naphthalene and 19 g (83 mmol) of 2-bromoisobutyryl bromide in 200 ml of CHZC12 via a solids metering funnel at room temperature in the course of minutes. After 4 hours, the mixture was worked up analogously to Example A. The crude product was filtered with ethyl acetate over a short column filled with silica gel. After the solvent had been stripped off, 15.5 g 25 (95~) of the isomer mixture 19a/19b were obtained as a yellowish oil. The isomer ratio of 19a:19b was 1:2.
1H-NMR spectrum (100 MHz, CDC13): 19a: 9.15 (m,lH), 7.40-8.10 (m,SH), 3.47 (dd,lH), 2.62-2.95 (m,2H), 1.37 (d,3H);
19b: 7.4-8.0 (m,6H), 3.7 (dd,lH), 2.75-3.10 (m,2H), 1.40 30 (d,3H).
Mass spectrum: 196 M+, correct disintegration pattern.

- 24 _ Example W
2-Methyl-6,7-benzoindan-1-one (19a) The same batch size as in Example V was chosen. The naphthalene was initially introduced into the reaction vessel together with the A1C13 in CHZC12, and bromoiso butyryl bromide was slowly added dropwise a~t room temper ature. After 1.5 hours, the mixture was worked up as in Example V. Chromatography on silica gel 60 with a hexane/ethyl acetate mixture gave 11 g (67~) of the indanone 19a.
Example X
2-Methyl-4,5-benzoindene (20a) and 2-methyl-6,7-benzo-indene (20b) 2.2 g (59.5 mmol) of sodium borohydride were added in portions to a solution of 7.8 g (39.7 mmol) of the isomer mixture of the indanones 19a/19b (Example V) in 400 ml of a tetrahydrofuran/methanol mixture (2:1) at room tempera-ture, and the mixture was stirred for 14 hours. The solution was poured onto ice-water acidified with HC1, and extracted with ether. The combined organic phases were washed several times with water and dried with sodium sulfate. The orange-colored oil which remained after the solvent had been stripped off was dissolved in 240 ml of toluene, and the solution was heated at 80°C
with 570 mg (3.15 mmol) of p-toluenesulfonic acid for 15 minutes. The solution was washed several times with water at room temperature, dried with sodium sulfate and evaporated. The residue was chromatographed on 300 g of silica gel 60. With a mobile phase mixture of hexane/
diisopropyl ether (20:1), 4.7 g (650) of 'the isomer mixture of the indenes 20a/20b in a ratio of 1:2 were able to be eluted (colorless oil).

1H-NMR spectrum (360 MHz, CDC13): isomer mixture 7.2-8.1 (m) , 7 . 05 (m) , 6 . 57 (m) , 3 . 57 ( s ) , 3. 42 (m) , 2 . 25 (d) , 2.20 (d).
Molecular weight: 180 M+, correct disintegration pattern.
Example Y
Dimethylbis(2-methyl-4,5-benzoindenyl)silane (21) 10.2 ml (25.5 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 4.6 g (25.5 mmol) of the isomer mixture of the indenes 20a/20b (Example X) in 50 ml of tetrahydrofuran at room temperature, and the mixture was heated under reflux for 1 hour. The red solution was then added dropwise to a solution of 1.55 g (12 mmol) of dimethyldichlorosilane in 10 ml of tetra-hydrofuran at room temperature, and the mixture was heated under reflux for 5-6 hours. The reaction solution was poured onto ice-water and extracted several times with ether. The combined organic phases were dried with sodium sulfate and evaporated, and the residue was dried under an oil-pump vacuum. The residue was chromatographed on 300 g of silica gel 60. With a mobile phase mixture of hexane/3~ ethyl acetate, 500 g of unreacted starting material 20a/20b were able to be eluted first. The ligand system 21 then followed with the same mobile phase. After the solvent had been stripped off, this ligand system was able to be crystallized by stirring with hexane. The yield was 1.7 g (34~ with respect to Si, or 44~ with respect to the 20a/20b reacted).
1H-NMR spectrum ( 100 MHz, CDC13 ) : diastereomers ( 1:1 ) 7 . 2 8.2 (m), 4.05 (s), 2.45 (d), 2.35 (d), -0.22 (s), -0.32 (s), -0.35 (s).
Mass spectrum: 416 M+, correct disintegration pattern and isotope pattern.

Sxample Z
rac-Dimethylsilanediylbis(2-methyl-4,5-benzoindenyl)-zircon:ium dichloride (22) 4.0 ml (10.2 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 1.? g (4.1 mmol) of the ligand system 21 in 20 ml of tetrahydrofuran at room temperature under Ar as the inert gas, and the mixture was stirred at room temperature for 14 hours. The residue which remained after 'the solvent had been stripped off was dried under an oil-pump vacuum and washed with hexane. The pale brown powder thus obtained was dried under an oil-pump vacuum at 40-50°C for several haurs, and added to a suspension of 1. 0 g ( 4 . 0 mmol ) of zir-conium tetrachloride in 25 ml of methylene chloride at -78°C. After the mixture had been warmed to room tempera-ture, the solvent was stripped off and the residue was extracted with 20 ml of toluene in order to remove the meso form of the zirconocene 22. The residue of the toluene extract was then extracted with 40 ml of methyle-ne chloride. The solution was concentrated to a small volume and left to crystallize at -35°C. A total of 970 mg (42~) of the zirconocene 22 were able to be isolated as the pure racemate in several fractions.
1H-NMR spectrum of the racemate (300 MHz, CDC13): 7.96 {2,m), 7.78 (2,m), 7.60 (2,d), 7.48-7.56 (4,m), 7.36 (2,d), 7.27 (2,s,~-Ind-H), 2.37 (6,s,Ind-CH3), 1.36 (6,s,Si-CH3). Mass spectrum: 574 M+, correct disinte gration, correct isotope pattern.
Example AA
2-Methyl-a-acenaphthindan-1-one (23) 29.7 g (129 mmol) of 2-bromoisobutyryl bromide were added to a solution of 20 g (129 mmol) of a-acenaphthene in 320 ml of methylene chloride at room temperature. 43.5 g ~f~~~~

(324 mmol) of A1C13 were then added via a solids metering funnel in the course of 15 minutes. After the mixture had been stirred for 30 minutes, it was poured into ice-water and extracted with methylene chloride. The organic phase was washed with water and an NaHC03 solution, and dried with NazS04. The residue which remained after the solvent had been stripped off was filtered over a short column with silica gel. 25 g (87~) of the indanone 23 were obtained with hexane/ethyl acetate (9:2).
1H-NMR {CDC13, 100 MHz): 8.57 (d, l), 7.60 (t,1), 7.35 {d,1), 7.25 (s, l), 3.45 (q, l), 3.40 {s,4), 2.60-2.95 (m,2), 1.35 (d,3).
Example BB
2-Methyl-a-acenaphthindene (24) A solution of 20 g (90 mmol) of the compound 23 in 250 ml of a tetrahydrofuran/methanol mixture (2:1) was added dropwise to a suspension of 3.8 g (100 mmol) of NaBH~ in 80 ml of tetrahydrofuran. The mixture was stirred at room temperature for 2 hours, and 100 ml of ethyl acetate and 100 ml of half-concentrated HC1 were added. The mixture was heated under reflux for ZO minutes and extracted with ethyl acetate. The organic phase was washed with water and dried with NazSO~ . On concentration and cooling to -35°C, a total of 16.3 g (88~k) of the compound 24 crys tallized in several fractions.
1H-NMR (CDC13, 100 MHz): 7.1-7.8 (m,4,aromatic-H), 6.97 (m,l,olefin-H), 3.37 {s,6,CH2), 2.25 (d,3,CH3).
Example CC
Dimethylbis{2-methyl-a-acenaphthindenyl)silane (25) 10.8 g (52.4 mmol) of the compaund 24 were deprotonated analogously to Example O and reacted with dimethyl-dichlorosilane. The organic phase was evaporated and the residue was chromatographed on silica gel. 6.2 g (51~) of the ligand system 25 were able to be obtained with hexane/4~ ethyl acetate.
1H-NMR (CDC13, 100 MHz): diastereomer pair 7.1-7.8 (m, aromatic-H), 4.0 (s,CH), 3.45 (s,CH2), 2.47 (d,CH3), 2.40 (d,CH3), -0.25 (s,SiCH3), -0.35 (s,SiCH3), -0.37 (s,SiCH3) .
Example DD
rac-Dimethylsilanediylbis(2-methyl-a-acenaphthindenyl)-zirconium dichloride (26) 4 . 9 g ( 10 . 5 mmol ) of the ligand system 25 were reacted analogously to Example P. The crude product, comprising the racemic form with the meso form in a ratio of 101, was recrystallized from chloroform. 1.3 g (20~) of the racemate 26 were obtained in the form of an orange-yellow powder.
1H-NMR (CDC13, 100 MHz)a 7.0-?.8 (m,aromatic-H), 3.1-3.4 (m,CH2) , 2.35 (s,CH3) , 1.35 (s,SiCH3) .
Polymerization examplesa Example 1 A dry 24 dm3 reactor was flushed with propylene and filled with 12 dm3 of liquid propylene. 35 cm~ of a toluene solution of methylaluminoxane (corresponding to 52 mmol of A1, average degree of oligomerization p = 20) were then added and the batch was stirred at 30°C for 15 minu-tes.
In parallel, 3.5 mg (0.005 mmol) of rac-dimethylsilyl(2-methyl-4,6-diisopropyl-1-indenyl)2zirconium dichloride were dissolved in 13.5 cm3 of a toluene solution of methylaluminoxane (20 mmol of Al) and preactivated by being left to stand for 15 minutes.

The wine-red solution was then introduced into the reactor, the mixture was heated to 75°C (10°C/minute) by supplying heat, and the polymerization system was kept at 70°C, by cooling, for 1 hour. The polymerization was stopped by gassing off the excess monomer. 2.11 kg of polypropylene were obtained.
The activity of the metallocene was thus 603 kg of polypropylene/g of metallocene x, hour.
Viscosity number = 259 cm3/g, MF, = 305, 000 g/mol; M,,,IMI, _ 2.0; isotactic index = 96.0'-k; bulk density = 400 g/dm3;
melt flow index (230/5) = 8.5 dg/minute.
Comparison Example 1 Example 1 was repeated with the metallocene rac-dimethyl-silyl(2-methyl-1-indenyl)ZZirconium dichloride. The metallocene activity was 395 kg of palypropylene/g of metallocene x hour.
Viscosity number = 159 cm3/g, M,p, = 158, 000 g/mol; MH,/M" _ 2.1 and the melt flow index (230/5) was 48 dg/minute. The isotactic index (IL) was 96Ø
Comparison Example 2 Example 1 was repeated with the metallocene rac-dimethyl-silyl(2-methyl-4-isopropyl-1-indenyl)ZZirconium dichloride.
The metallocene activity was 460 kg of polypropylene/g of metallocene x hour, viscosity number = 152 cm3/g, 1~, _ 147,500 g/mol, M~,/M" = 2.3 and melt flow index (230/5) _ 51 dg/minute.

_ 30 Comparison Example 3 Example Z was repeated with rac-dimethylsilyl(1-inde-nyl)ZZirconium dichloride. The metallocene activity was 695 kg of polypropylene/g of mei:allocene x hour.
Viscosity number = 31 cm3/g, MH, = 18,500 g/mol, M~"/MI, _ 2.2, melt flow index (230/5) wa:~ no longer measurable.
Comparison Example 4 Example 1 was repeated with the metallocene rac-dimethyl-silyl(4,7-dimethyl-1-indenyl)ZZirconiurn dichloride. The metallocene activity was 195 kg of polypropylene/g of metallocene x hour, viscosity number - 16 cm3/g, M~" _ 9,500 g/mol, M~",/M" = 2.0, II = 87~, the melt flow index (230/5) was not measurable.
The four comparison experiments show that polypropylenes prepared with the metallocenes substituted in various ways on the indenyl ligand and prepared with the unsub-stituted metallocene show significant differences in molecular weight. Including the metallocene according to the invention from Example 1, the range extends from the wax range (Comparison Example 4) to the very high mole-cular weight polymer according to the invention (Example 1).
These experiments demonstrate the superiority of the metallocenes substituted in the 2,4,6-position.

Claims (13)

1. A compound of the formula VI having indenyl ligands which are substituted on the five- and on the six-membered ring and in the 2,6-, 2,4,6-, 2,4,5-,

2,4,5,6-, or 2,4,5,6,7-, position in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1, R2, R3, R4 AND R5 are identical of different and are hydrogen, (C1-C20)alkyl, (C6-C14)aryl, (C1-C10)alkoxy, (C2-C10)alkenyl, (C7-C20)arylalkyl, (C7-C20)alkylaryl, (C6-C10)aryloxy, (C1-C10)fluoroalkyl, (C6-C10)halo-genoaryl, (C2-C10)alkynyl, a radical -SiR6 3, in which R6 is (C1-C10)alkyl, a halogen atom or a heteroaromatic radical which has 5 or 6 ring members and can contain one or more hetero atoms, or adjacent radicals R1-R4, with the atoms joining them, form one or more rings, with the proviso that R1 and R2 with the atoms joining them cannot form a phenyl ring, R7 is a radical in which M2 is a carbon, silicon, germanium or tin, R8 and R9 are identical or different and are hydrogen, (C1-C20)alkyl, (C6-C14)aryl, (C1-C10)alkoxy, (C2-C10) alkenyl, (C7-C20) arylalkyl, (C7-C20)alkylaryl, (C6-C10) aryloxy, (C1-C10)fluoroalkyl, (C6-C10)halogenoaryl, (C2-C10)alkynyl or halogen, or R8 and R9, together with the atom joining them, from a ring, p is 0, 1, 2 or 3 and R10 and R11 are identical or different and are hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy, (C6-C10)aryl, (C6-C10) aryloxy, (C2-C10)alkenyl, (C7-C40)arylalkyl, (C7-C40) alkylaryl, (C8-C40)arylalkenyl, hydroxy or a halogen atom.

2. The compound of the formula VI as claimed in claim 1, in which M1 is zirconium or hafnium, R1, R2, R3 and R4 are identical or different and are hydrogen, (C1-C10)alkyl, (C6-C14)aryl, (C1-C4)alkoxy, (C2-C6)alkenyl, (C1-C6)fluoroalkyl, a halogen atom or a heteroaromatic radical which has 5 or 6 ring members and can contain one or more hetero atoms, or adjacent radicals R1-R4, with the atoms joining them, form a ring, with the proviso that R1 and R2 with the atoms joining them cannot form a phenyl ring, and R5 is (C1-C10)alkyl, M2 is carbon or silicon, R8 and R9 are identical or different and are hydrogen (C1-C6)alkyl, (C6-C10)aryl, (C1-C6)alkoxy, (C2-C4)alkenyl, (C7-10)arylalkyl or (C7-C10)alkylaryl, or R8 and R9, together with the atom joining them, form a ring, p is 1 or 2, and R10 and R11 are identical or different and are hydrogen (C1-C3)alkyl, (C1-3)alkoxy, (C6-C8)aryl, (C6-C8) aryloxy, (C2-C4)alkenyl, (C7-10)arylalkyl, (C7-10) alkylaryl, (C8-C12)arylalkenyl or a halogen atom.

3. The compound of the formula VI as claimed in claim 2, wherein M1 is zirconium.

4. The compound of the formula VI as claimed in claim 2 or 3, wherein M2 is silicon.

5. The compound of the formula VI as claimed in any one of claims 2-4, wherein p is 1.

6. The compound of the formula VI as claimed in any one of claims 2-5, wherein the (C1-C3) alkyl in the definition of R10 and R11 is methyl.

7. The compound of the formula VI as claimed in any one of claims 2-6, wherein the halogen atom in the definition of R10 and R11 is chlorine.

8. The compound of the formula VI as claimed in any one of claims 1-3, in which M2 is silicon and R8 and R9 are identical or different and are (C1-C6)alkyl or (C6-C10)aryl.

9. The compound of the formula VI as claimed in any one of claims 1-8, in which the indenyl radicals in formula VI are substituted in the 2,4,6- and 2, 4, 5-position.

10. The compound of the formula VI as claimed in claim 9, in which the indenyl radicals in formula VI
are substituted by (C1-C4)alkyl.

11. Use of a compound of the formula VI as defined in any one of claims 1-10 as a catalyst component in olefin polymerization.

12. A catalyst comprising a) a compound of the formula VI
claimed in any one of claims 1-10 and b) a cocatalyst.

13. A process for the preparation of an olefin polymer in the presence of a catalyst as in claim 12.