Patent Description:
Metallocene complexes together with a cocatalyst form catalysts that are widely used for olefin polymerisation. In general, the metallocene complexes are known to have only one active polymerisation center and are often referred to as single site catalysts or discrete catalysts to distinguish them from non-single site catalysts like for instance Ziegler-type catalysts. The presence of one active center is believed to result in polymers having a narrow molecular weight distribution (MWD) and narrow compositional distribution for copolymers of different olefins. An advantage of metallocene catalysts is their high activity and well defined structures compared to traditional Ziegler-Natta catalysts. A further advantage of metallocene catalysts over conventional Ziegler-type catalysts is that the former can display a higher reactivity towards alpha-olefins, which is especially beneficial in copolymerisations of ethylene with such alpha-olefins. Catalysts with a high reactivity towards alpha-olefins require less alpha-olefin during the polymerisation in order to reach a desired alpha-olefin content in the final polymer, which is an advantage in the commercial preparation of copolymers of ethylene with alpha-olefins.

It is well known in the art that the reactivity of alpha-olefins compared to ethylene decreases upon increasing the size of the alpha-olefin. For instance, the reactivity decreases from propylene > <NUM>-butene > <NUM>-hexene > <NUM>-octene, as has been published for example by Krentsel et al in <NPL> and by <NPL>. Therefore, especially when copolymerising ethylene with higher alpha-olefins like <NUM>-hexene, catalysts are needed that display a high reactivity towards such alpha-olefins.

LLDPE polymers are disclosed in <CIT> and <CIT>.

An additional complication arises in the preparation of copolymers of ethylene and alpha-olefins, which is related to the general observation that the average molecular weight of the obtained copolymers tends to decrease upon increasing alpha-olefin content, which for example has been published by <NPL>. The combination of high comonomer reactivity as well as high molecular weight is a challenging target for developing commercially applicable metallocene catalysts.

Numerous patent applications are known describing metallocene catalysts. For example, <CIT> describes metallocene catalysts for the polymerisation of ethylene to branched polyethylene using a catalyst containing the metallocene system dimethylsilylene(<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-cyclopentadienyl)(<NUM>-phenyl-<NUM>-indenyl)zirconium dichloride. <CIT> discloses a metallocene catalyst with an ethylene bridged <NUM>-indenyl <NUM>-indenyl zirconium complex. <CIT> discloses <NUM>-indenyl complexes for olefin polymerisation. <CIT> describes a <NUM>-indenyl bridged catalyst system. <NPL>) describes an investigation of bridge and <NUM>-phenyl substituent effects on ethylene -alfa olefin copolymerisation behavior with dimethylsilyl bridged bis <NUM>-indenyl/<NUM>-indenyl zirconium complexes.

Metallocenes bearing <NUM>-indenyl ligands are known in the art. For example, <CIT> (SABIC/DSM) describes <NUM>-indenyl containing bridged metallocenes, in which the bridge contains an sp2 hybridized carbon. <NPL>et al) describes <NUM>,<NUM> ethylene bridged bis-<NUM>-indenyl zirconocenes. These metallocene catalysts result in polymers having a low molecular weight. <NPL>et al) describes <NUM>,<NUM>-naphthylidene bridged metallocenes. In this publication it is stated that <NUM>,<NUM>-naphthylidene bridged metallocenes containing a fluorenyl and a <NUM>-indenyl ligand result in lower molecular weight polyethylene compared to its fluorenyl/<NUM>-indenyl or fluorenyl/ cyclopentadienyl containing analogues. <CIT>) describes methylene bridged bis-<NUM>-indenyl zirconocenes, which also give polymers having a low molecular weight.

Despite all efforts, there is a need for a highly active catalyst, which is able to produce polyolefins in a high yield, having a high reactivity for alpha olefin incorporation (like for example copolymerisation of ethylene with <NUM>-hexene) and which is still giving high molecular weight polymers.

A new family of metallocene complexes has now been discovered which advantageously can be used for olefin polymerisation, preferably for ethylene copolymerisation, and which gives at least one advantage of a higher catalyst activity, a higher <NUM>-hexene incorporation and/or a high molecular weight polymer.

The invention relates to a metallocene complex according to formula I,
<CHM>
wherein R<NUM> and R<NUM> are independently selected from H, an alkyl or an aryl group, wherein R<NUM> is a C1-C10 alkyl group, wherein R' is selected from H, an alkyl group, an aryl group and wherein different R' substituents can be connected to form a ring structure and wherein B is a <NUM>,<NUM> phenylene bridging moiety or a substituted <NUM>,<NUM>-phenylene bridging moiety substituted on the <NUM>, <NUM>, <NUM> or <NUM> position with alkyl or aryl groups, wherein Mt is selected from Ti, Zr and Hf, X is an anionic ligand, z is the number of X groups and equals the valence of Mt minus <NUM>. For example, X may be a halogenide, an alkoxide, an alkyl group, an aryl group or an aralkyl group.

The metallocene complex according to the invention surprisingly can copolymerise ethylene with alpha olefins in a high yield with a very high <NUM>-hexene reactivity and a very high molecular weight. This copolymerisation can take place in the presence of a cocatalyst and under suitable polymerisation conditions.

The metallocene complex according to the present invention has the general structure according to formula I:
<CHM>.

R<NUM> and R<NUM> are preferably independently selected from H, a C1-C10 alkyl group or a C6-C10 aryl group. Examples of suitable alkyl groups are methyl, ethyl, n-propyl, iso-propyl, butyl, pentyl, hexyl, octyl, decyl and the like. Examples of suitable aryl groups are substituted or unsubstituted phenyl and naphthyl groups, preferably phenyl groups, or <NUM>,<NUM>-dimethyl-<NUM>-phenyl, <NUM>,<NUM>-diethyl-<NUM>-phenyl,<NUM>,<NUM>-diisopropyl-<NUM>-phenyl or <NUM>,<NUM>-ditertiairbutyl-<NUM>-phenybenzyl. More preferably, R<NUM> and R<NUM> are chosen from H, a methyl, ethyl, n-propyl or iso-propyl group, a butyl group, a hexyl or cyclohexyl group, or a phenyl group. Most preferably, R<NUM> and R<NUM> are chosen from H, methyl or phenyl groups.

R<NUM> is preferably a C1-C4 alkyl group, more preferably a methyl, ethyl, n-propyl or iso-propyl group, most preferably selected from a methyl or isopropyl group.

Preferably Mt is zirconium or hafnium, most preferably Mt is zirconium.

Preferably X is a monovalent anionic group, selected from the group consisting of halogen (F, CI, Br or I), a C1-C20 hydrocarbyl group or a C1-C20 alkoxy group. Preferably X is a methyl group, CI, Br or I, most preferably methyl or Cl.

The metallocene complex according to formula (I) comprises a <NUM>-substituted <NUM>-indenyl group which is bridged through a <NUM>,<NUM>-phenylene bridge to a <NUM>-indenyl group, which <NUM>-indenyl group can be substituted with one or more substituents on the <NUM> and <NUM> position. Both <NUM>-indenyl and <NUM>-indenyl ligands can be further substituted on the <NUM> membered indenyl ring with alkyl or aryl substituents.

The <NUM>,<NUM> phenylene bridge can be substituted on the <NUM>, <NUM>, <NUM> or <NUM> position with alkyl or aryl groups. Preferably the bridge is a <NUM>,<NUM> phenylene bridge as shown in structure (II). In the context of the present invention, the <NUM>,<NUM> phenylene bridge may be a bridging moiety comprising a phenylene group that is bound to a <NUM>-indenyl ligand or a first of either the <NUM> or <NUM> position of the phenylene group, and to a <NUM>-indenyl ligand at the other of the <NUM> or <NUM> position of the phenylene group, wherein further the phenylene group may be substituted on the <NUM>,<NUM>,<NUM> or <NUM> position with alkyl or aryl groups.

The metallocene complex can be immobilized on a support. The support is preferably an inert support, more preferably a porous inert support. Examples of porous inert supports materials are talc, clay and inorganic oxides. Preferably, the support material is in a finely divided form.

Suitable inorganic oxide materials include group 2A, 3A, 4A and 4B metal oxides such as silica, alumina and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica or alumina are magnesia, titania, zirconia and the like. Other support materials, however, can be employed, for example finely divided functionalized polyolefins such as finely divided polyethylene or polystyrene.

Preferably, the support is a silica having a surface area between <NUM> and <NUM><NUM>/g and a pore volume between <NUM> and <NUM>/g.

The invention is also directed to a catalyst prepared from the metallocene complex according to the invention and a cocatalyst. The cocatalyst should be capable to generate a cationic specie from the metallocene compound and form a so-called non- or weakly coordinating anion. Suitable cocatalysts include aluminium- or boron-containing cocatalysts. Suitable aluminium-containing cocatalysts comprise aluminoxanes, alkyl aluminium compounds and aluminium-alkyl-chlorides. The aluminoxanes usable according to the present invention are well known and preferably comprise oligomeric linear and/or cyclic or cage-like alkyl aluminoxanes represented by the formula: R<NUM> - (AlR<NUM> -O)n - AlR<NUM><NUM> for oligomeric, linear aluminoxanes and (- AlR<NUM> - O -)m for oligomeric, cyclic aluminoxanes; wherein n is <NUM>-<NUM>, preferably n is <NUM>-<NUM>; m is <NUM>-<NUM>, preferably m is <NUM>-<NUM> and R<NUM> is a C<NUM> to C<NUM> alkyl group and preferably a methyl group. Further other organoaluminium compounds can be used such as trimethylaluminium, triethylaluminium, triisopropylaluminium, tri-n-propylaluminium, triisobutylaluminium, tri-n-butylaluminium, tri-tert-butylaluminium, triamylaluminium; dimethylaluminium ethoxide, diethylaluminium ethoxide, diisopropylaluminium ethoxide, di-n-propylaluminium ethoxide, diisobutylaluminium ethoxide and di-n-butylaluminium ethoxide; dimethylaluminium hydride, diethylaluminium hydride, diisopropylaluminium hydride, di-n-propylaluminium hydride, diisobutylaluminium hydride and di-n-butylaluminium hydride.

Suitable boron-containing cocatalysts include trialkylboranes, for example trimethylborane or triethylborane and/or perfluoroarylborane and/or perfluoroarylborate-compounds.

In the process to produce olefin polymers by polymerising one or more olefins in the presence of a metallocene complex preferably an organoaluminium cocatalyst is present.

More preferably, methylaluminoxane, trialkylboranes, perfluoroarylboranes or perfluoroarylborates are used as the cocatalyst.

In another aspect, the invention relates to a process for the preparation of olefin polymers by polymerising one or more olefins in the presence of a cocatalyst and the metallocene complex of the invention, wherein the metallocene complex optionally is immobilized on a support.

The process to produce the olefin polymers may start with the reaction of the metallocene complex according to the invention with the cocatalyst. This reaction can be performed in the same vessel as the reaction vessel wherein the olefin polymers are produced or in a separate vessel, whereafter the mixture of the metallocene complex and the cocatalyst is fed to the reaction vessel. During the reaction described above an inert solvent can be used.

The polymerisation, can be adequately carried out in a slurry process, a solution process or a gas-phase process.

In the mixture of the metallocene complex and an organoaluminium cocatalyst, the cocatalyst is used in an amount of <NUM> to <NUM>,<NUM> mol, preferably from <NUM> to <NUM>,<NUM> mol per mol of the transition metal compound.

In the mixture of the metallocene complex and an organoborane or organoborate cocatalyst, the cocatalyst is used in an amount of <NUM>,<NUM> to <NUM> mol, preferably from <NUM>,<NUM> to <NUM> mol per mol of the transition metal compound.

The solvent used in a slurry process to produce olefin polymers may be any organic solvent usually used for the polymerisation. Examples of solvents are benzene, toluene, xylene, propane, butane, pentane, hexane, heptane, cyclohexane and methylene chloride. Also the olefin to be polymerised can be used as the solvent.

In the polymerisation process, an additional compound can be used as a scavenger compound to scrub undesirable impurities from the polymerisation medium that can adversely affect the catalyst productivity. Examples of such undesired impurities are oxygen, water, alcohols and the like. Suitable scavenging agents are metal alkyl compounds, such as aluminium alkyl, magnesium alkyl, or zinc alkyl compounds. The aluminium alkyl compound for the purpose of scavenging the impurities can also be an aluminoxane compound. Also partially pacified aluminium alkyl compounds can be used. For instance, the reaction product of an aluminium alkyl with a sterically hindered phenol can be used.

In the process to produce olefin polymers the polymerisation conditions, like for example temperature, time, pressure, monomer concentration can be chosen within wide limits. The polymerisation temperature is in the range from -<NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>. The polymerisation time is in the range of from <NUM> seconds to <NUM> hours, preferably from <NUM> minute to <NUM> hours, more preferably from <NUM> minutes to <NUM> hours. The ethylene pressure during polymerisation is in the range from <NUM> to <NUM> bar, preferably from <NUM> to <NUM> bar, more preferably from <NUM> to <NUM> bar, even more preferably from <NUM> to <NUM> bar, most preferably from <NUM> to <NUM> bar. The molecular weight of the polymer can be controlled by use of hydrogen in the polymerisation. The polymerisation may be conducted by a batch process, a semi-continuous process or a continuous process and may also be conducted in two or more steps of different polymerisation conditions. The polyolefin produced is separated from the polymerisation solvent and dried by methods known to a person skilled in the art.

In the process to produce olefin polymers the olefin which is polymerised can be one type of olefin or can be mixtures of different olefins. The polymerisation thus includes homopolymerisation and copolymerisation. Examples of olefins are α-olefins such as ethylene, propylene, <NUM>-butene, <NUM>-pentene, <NUM>-methyl-<NUM>-butene, <NUM>-methyl-<NUM>-pentene, <NUM>-methyl-<NUM>-pentene, <NUM>-hexene, <NUM>-octene, <NUM>-nonene, <NUM>-decene; conjugated and non-conjugated dienes such as butadiene, <NUM>,<NUM>-hexadiene, <NUM>-ethylidene-<NUM>-norbornene, dicyclopentadiene, <NUM>-methyl-<NUM>,<NUM>-hexadiene and <NUM>-methyl-<NUM>,<NUM>-octadiene; cyclic olefins such as cyclobutene and other olefinic compounds such as isobutene, vinyl-cyclohexane and styrene but is not limited thereto.

Preferably, at least one of the olefins that is polymerised is ethylene. More preferably, a mixture of ethylene and at least one other α-olefin of <NUM> or more carbon atoms is polymerised.

Preferably, the other olefin of <NUM> or more carbon atoms is chosen from <NUM>-butene, <NUM>-hexene, <NUM>-octene, vinyl-cyclohexane or <NUM>-methyl-<NUM>-pentene.

Preferably, the olefin comonomer is present in an amount of about <NUM> to about <NUM> percent by weight in the ethylene-olefin copolymer, more preferably an amount of from about <NUM> to about <NUM> percent by weight in the ethylene α-olefin copolymer.

For example, a linear low density polyethylene (LLDPE) having a melt mass flow rate (also known as melt flow index) as determined using ASTM D1238-<NUM> (<NUM>/<NUM>) which ranges from <NUM> to <NUM>/<NUM> and a density in the range from <NUM>/m<NUM> to less than <NUM>/m<NUM> as determined using ASTM D1505-<NUM> may be obtained. For example, the density of the LLDPE ranges from about <NUM>/m<NUM> to less than <NUM>/m<NUM>, for example between <NUM> and <NUM>/m<NUM>. For example, the melt flow index of the LLDPE ranges from <NUM> to <NUM>/<NUM>, for example from <NUM> to <NUM>/<NUM>.

The polymerisation may be performed via a gas-phase process, via a slurry process or via a solution process. The production processes of polyethylene are summarised in "<NPL>.

The various processes may be divided into solution polymerisation processes employing homogeneous (soluble) catalysts and processes employing supported (heterogeneous) catalysts. The latter processes include both slurry and gas phase processes.

When carrying out a slurry or gas phase process, a so-called continuity agent or antistatic agent or anti-fouling agent may be added to reactor.

The invention is also directed to a polyolefin, for example polyethylene, preferably high density polyethylene (HDPE) obtainable or obtained by the process of the invention, for example by copolymerising ethylene and at least one other olefin in the presence of a metallocene complex according to the invention or a composition, wherein the metallocene complex according to the invention is immobilized on a support.

As defined herein, in linear low density polyethylene, the term "linear" means that the polymer is substantially linear, but may contain some long chain branching.

"Long chain branching" (LCB) means a chain length longer than the short chain branch that results from the incorporation of the α-olefin(s) into the polymer backbone. Each long chain branch will have the same comonomer distribution as the polymer backbones and can be as long as the polymer backbone to which it is attached.

As a practical matter, current <NUM>C nuclear magnetic resonance spectroscopy cannot distinguish the length of a long chain branch in excess of six carbon atoms. However, there are other known techniques useful for determining the presence of long chain branches in ethylene polymers. Two such methods are gel permeation chromatography coupled with a low angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography coupled with a differential viscometer detector (GPC-DV). In addition, melt-rheology, for example determining the behavior of the polymer melt under different shear rates, is frequently used to indicate the presence of long chain branching. The use of these techniques for long chain branch detection and the underlying theories have been well documented in the literature.

It has been found that with the metallocene complex of the invention or with the composition of the invention wherein the metallocene complex of the invention is present on a support, it is possible to produce polyethylene from ethylene and at least one other olefin, for example an olefin having up to <NUM> carbon atoms, with a high incorporation of the at least one other olefin.

The amount of incorporation of the at least one other olefin, for example an α-olefin in the polyethylene is expressed by the amount of branches per <NUM> carbon atoms.

The presence of short chain branching of up to <NUM> carbon atoms in length can be determined in ethylene polymers by using <NUM>C nuclear magnetic resonance (NMR) spectroscopy and is quantified using the method described by <NPL>).

Therefore, the invention also relates to a polyolefin, preferably polyethylene, for example linear low density polyethylene (LLDPE). The low density polyethylene, for example LLDPE, preferably has an amount of branches per <NUM> carbon atoms as determined using <NUM>C NMR of at least <NUM>, for example of at least <NUM>, for example at least <NUM> and/or for example at most <NUM>, for example at most <NUM>, for example at most <NUM>, for example at most <NUM>.

The number average molecular weight (Mn) of the polyolefin, for example polyethylene, for example LLDPE of the invention may vary between wide ranges and may for example be in the range from <NUM> to <NUM> Da.

For example, the Mn of the polyolefin of the invention may be at least <NUM>, for example at least <NUM>, for example at least <NUM>,<NUM>, for example at least <NUM>,<NUM> and/or for example at most <NUM>,<NUM>, for example at most <NUM>,<NUM>, for example at most <NUM>,<NUM>, for example at most <NUM>,<NUM> Da.

The weight average molecular weight (Mw) of the polyolefin, for example polyethylene, for example LLDPE of the invention may also vary between wide ranges and may for example be in the range from <NUM> to <NUM>. For example, the Mw of the polyolefin of the invention may be at least <NUM>, for example at least <NUM>,<NUM>, for example at least <NUM>,<NUM>, for example at least <NUM>,<NUM> and/or for example at most <NUM>,<NUM>, for example at least <NUM>,<NUM>, for example at most <NUM>,<NUM>, for example at most <NUM>,<NUM>.

For purpose of the invention, the Mw and Mn are determined using SEC (Size Exclusion Chromatography) using <NUM>,<NUM>,<NUM>-trichlorobenzene or o-dichlorobenzene as an eluent, and calibrated using linear polyethylene or polystyrene standards.

The molecular weight distribution (that is Mw/Mn) of the polyolefin of the invention may for example vary from <NUM> to <NUM>, from <NUM> to <NUM> or from <NUM> to <NUM>.

The polyolefin obtained or obtainable by the process of the invention may be mixed with suitable additives.

Examples of suitable additives for polyethylene include but are not limited to the additives usually used for polyethylene, for example antioxidants, nucleating agents, acid scavengers, processing aids, lubricants, surfactants, blowing agents, ultraviolet light absorbers, quenchers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, pigments, dyes and fillers, and cure agents such as peroxides. The additives may be present in the typically effective amounts well known in the art, such as <NUM> weight % to <NUM> weight % based on the total composition.

The polyolefins of the invention and compositions comprising said polyolefins may suitably be used for the manufacture of articles. For example, the polyolefins and compositions of the invention may be manufactured into film, for example by compounding, extrusion, film blowing or casting or other methods of film formation to achieve, for example uniaxial or biaxial orientation. Examples of films include blown or cast films formed by coextrusion (to form multilayer films) or by lamination and may be useful as films for packaging, for example as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and non-food contact applications, agricultural films and sheets.

Therefore, in another aspect, the invention also relates to articles comprising the polyolefins obtainable by the process of the invention.

In yet another aspect, the invention also relates to use of the polyolefins obtainable by the process of the invention for the preparation of articles, for example for the preparation of films.

In yet another aspect, the invention relates to a process for the preparation of articles using the polyolefin according to the invention.

It is further noted that the term 'comprising' does not exclude the presence of other elements. However, it is also to be understood that a description on a product comprising certain components also discloses a product consisting of these components. Similarly, it is also to be understood that a description on a process comprising certain steps also discloses a process consisting of these steps.

The invention will hereafter be elucidated by way of the following examples, without being limited thereto.

All manipulations were carried out under an atmosphere of dry, O<NUM>-free N<NUM> employing an Innovative Technology glove box and a Schlenk vacuum-line. Tetrahydrofuran (THF), toluene, methylene chloride, hexane and pentane were purified with a Grubbs-type column system manufactured by Innovative Technology and dispensed into thick-walled Schlenk glass flasks equipped with Teflon-valve stopcocks. Pyridine was dried over the appropriate agents and distilled into the same kind of storage flasks. Anhydrous benzene (Alfa, <NUM>%, packaged under argon) was purchased and used as received. Deuterated solvents were dried over the appropriate agents, vacuum-transferred into storage flasks with Teflon stopcocks and degassed accordingly (CDCl<NUM>, C<NUM>D<NUM> and CD<NUM>Cl<NUM>). <NUM>H, <NUM>B, <NUM>C and <NUM>P NMR spectra were recorded at <NUM> Bruker <NUM> spectrometers. Chemical shifts are given relative to SiMe<NUM> and referenced to the residue solvent signal (<NUM>H, <NUM>C). <NUM>B and <NUM>P resonances were referenced externally to (BF<NUM>•Et<NUM>O) and <NUM>% H<NUM>PO<NUM>, respectively. Chemical shifts are reported in ppm and coupling constants as scalar values in Hz. ZrCl<NUM>(Me<NUM>S)<NUM>,<NUM> TiCl<NUM>(THF)<NUM><NUM> and TiCl<NUM>(Me<NUM>S)<NUM><NUM> were prepared as reported in, respectively, <NPL>; <NPL> and <NPL>. ZrCl<NUM>(THF)<NUM> (Strem) was purchased and used as received.

A mixture of <NUM> (<NUM> mmol) of <NUM>-phenylethanone and <NUM> (<NUM> mmol) of <NUM>-bromobenzaldehyde was added dropwise to a solution of <NUM> of NaOH in a mixture of <NUM> of <NUM>% EtOH and <NUM> of water. The resulting mixture was stirred for <NUM> at r. , then, diluted with <NUM> of water and extracted with <NUM>×<NUM> of dichloromethane. The combined extract was dried over K<NUM>CO<NUM>, passed through a short pad of silica gel <NUM> (<NUM>-<NUM>) and evaporated to dryness. The residue was distilled in vacuum (b. <NUM>-<NUM>/<NUM> Pa (<NUM> Hg)) to afford <NUM> (<NUM>%) of (2E)-<NUM>-(<NUM>-bromophenyl)-<NUM>-phenylprop-<NUM>-en-<NUM>-one.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (dd, J = <NUM>, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (tm, J = <NUM>, <NUM>), <NUM> (td, J = <NUM>, J = <NUM>, <NUM>).

To polyphosphoric acid (prepared from <NUM> of P<NUM>O<NUM> and <NUM> of <NUM>% H<NUM>PO<NUM>) <NUM> (<NUM> mmol) of (2E)-<NUM>-(<NUM>-bromophenyl)-<NUM>-phenylprop-<NUM>-en-<NUM>-one were added at <NUM> and the resulting mixture was stirred at this temperature for <NUM>. Then, it was poured onto <NUM> of ice. The product was extracted with <NUM>×<NUM> of dichloromethane. The combined extract was washed with aqueous solution of K<NUM>CO<NUM>, dried over K<NUM>CO<NUM>, passed through a short pad of silica gel <NUM> (<NUM>-<NUM>) and evaporated to dryness. The residue was purified by column chromatography on silica gel <NUM> (<NUM>-<NUM>; eluent: hexanes/dichloromethane = <NUM>:<NUM>, vol. , then dichloromethane/EtOAc = <NUM>:<NUM>, vol. This procedure gave <NUM> (<NUM>%) of <NUM>-(<NUM>-bromophenyl)indan-<NUM>-one as a white solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (dd, J = <NUM>, J = <NUM>, <NUM>), <NUM> (dd, J = <NUM>, J = <NUM>, <NUM>), <NUM> (dd, J = <NUM>, J = <NUM>, <NUM>).

To a mixture of <NUM> (<NUM> mmol) of <NUM>-(<NUM>-bromophenyl)indan-<NUM>-one and <NUM> (<NUM> mmol) of NaBH<NUM> in <NUM> of THF <NUM> of methanol were added dropwise for <NUM> at <NUM>. This mixture was stirred overnight at r. and then evaporated to dryness. The residue was partitioned between <NUM> of dichloromethane and <NUM> of <NUM> HCl. The organic layer was separated, and the aqueous layer was additionally extracted with <NUM> of dichloromethane. The combined organic extract was dried over Na<NUM>SO<NUM> and evaporated to dryness to give a white mass. To a solution of thus obtained <NUM>-(<NUM>-bromophenyl)indan-<NUM>-ol in <NUM> of DMSO <NUM> (<NUM> mol) of KOH and <NUM> (<NUM> mol) of Mel were added. This mixture was stirred for <NUM> at ambient temperature. The formed solution was decanted from an excess of KOH, the latter was additionally washed with <NUM>×<NUM> of dichloromethane. The combined organic solution was washed with <NUM> of water. The organic layer was separated, and the aqueous layer was extracted with <NUM>×<NUM> of dichloromethane. The combined organic extract was washed with <NUM>×<NUM> of water, dried over Na<NUM>SO<NUM>, and then evaporated to dryness. The residue was purified by column chromatography on silica gel <NUM> (<NUM>-<NUM>; eluent: hexanes/dichloromethane = <NUM>:<NUM>, vol. , then <NUM>:<NUM>, vol. This procedure gave <NUM> (<NUM>%) of <NUM>-(<NUM>-bromophenyl)-<NUM>-methoxyindane as a white solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>).

To a solution of <NUM> (<NUM> mmol) of <NUM>-(<NUM>-bromophenyl)-<NUM>-methoxyindane in <NUM> of THF <NUM> (<NUM> mmol) of <NUM> n-butyllithium in hexanes were added dropwise at -<NUM> over <NUM>. This mixture was stirred for <NUM> at -<NUM>, then the resulting solution was cooled to -<NUM>, and <NUM> (<NUM> mmol) of trimethyl borate was added in one portion. The reaction mixture was stirred overnight at r. , then it was quenched by addition of <NUM> of 2N hydrochloric acid. The resulting mixture was stirred for <NUM>, then extracted with <NUM>×<NUM> of ether. The combined extract was evaporated and dried in vacuum to give yellowish oil. To the solution of this oil in <NUM> of THF <NUM> (<NUM> mmol) of pinacol were added and this mixture was stirred at r. overnight, then, additionally for <NUM> at reflux. After evaporation, the crude product was purified by column chromatography on silica gel <NUM> (<NUM>-<NUM>; eluent: hexanes/dichloromethane = <NUM>:<NUM>, vol. , then <NUM>:<NUM>, vol. This procedure gave <NUM> (<NUM>%) of <NUM>-[<NUM>-(<NUM>-methoxy-<NUM>,<NUM>-dihydro-<NUM>-inden-<NUM>-yl)phenyl]-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM>-dioxaborolane as a white solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (dd, J = <NUM>, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (td, J = <NUM>, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (ddd, J = <NUM>, J = <NUM>, J = <NUM>, <NUM>), <NUM> (ddd, J = <NUM>, J = <NUM>, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

A mixture of <NUM> (<NUM> mmol) of <NUM>-[<NUM>-(<NUM>-methoxy-<NUM>,<NUM>-dihydro-<NUM>-inden-<NUM>-yl)phenyl]-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM>-dioxaborolane, <NUM> (<NUM> mmol) of <NUM>-(<NUM>-bromophenyl)-<NUM>H-indene, <NUM> (<NUM> mmol) of Na<NUM>CO<NUM>, <NUM> (<NUM> mmol, <NUM> mol. %) of Pd(PtBu<NUM>)<NUM>, <NUM> of water and <NUM> of <NUM>,<NUM>-dimethoxyethane (DME) was refluxed for <NUM>. DME was evaporated on a rotary evaporator, and <NUM> of water and <NUM> of dichloromethane were then added to the residue. The organic layer was separated, and the aqueous layer was additionally extracted with <NUM> of dichloromethane. The combined extract was dried over K<NUM>CO<NUM> and then evaporated to dryness to give a dark-red solid. The crude product was purified by flash chromatography on silica gel <NUM> (<NUM>-<NUM>, hexane/dichloromethane = <NUM>:<NUM>, vol. , then, <NUM>:<NUM>, vol. ) to give <NUM> (<NUM>%) of <NUM>-(<NUM>-inden-<NUM>-yl)-<NUM>'-(<NUM>-methoxy-<NUM>,<NUM>-dihydro-<NUM>-inden-<NUM>-yl)biphenyl as a yellowish oil which completely solidified at r.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, J = <NUM>) and <NUM> (dd, J = <NUM>, J = <NUM>) {sum <NUM>}, <NUM>-<NUM> (m, <NUM>), <NUM> (s) and <NUM> (d, J = <NUM>) {sum <NUM>}, <NUM> (t, J = <NUM>) and <NUM> (t, J = <NUM>) {sum <NUM>}, <NUM> (t, J = <NUM>) and <NUM> (t, J = <NUM>) {sum <NUM>}, <NUM>-<NUM> (<NUM> and m, <NUM>), <NUM>-<NUM> (m) and <NUM>-<NUM> (m) {sum <NUM>}, <NUM>-<NUM> (m, <NUM>).

To a solution of <NUM> (<NUM> mmol) of <NUM>-(<NUM>-inden-<NUM>-yl)-<NUM>'-(<NUM>-methoxy-<NUM>,<NUM>-dihydro-<NUM>-inden-<NUM>-yl)biphenyl in <NUM> of toluene <NUM> of TsOH was added, and this mixture was refluxed with Dean-Stark head for <NUM> and then cooled to r. The resulting solution was washed with <NUM>% aqueous Na<NUM>CO<NUM>. The organic layer was separated and the aqueous layer was extracted with <NUM>×<NUM> of dichloromethane. The combined organic solution was dried over K<NUM>CO<NUM> and then passed through a short pad of silica gel <NUM> (<NUM>-<NUM>). The silica gel pad was additionally washed with <NUM> of dichloromethane. The filtrate was evaporated almost to dryness and the residue was dissolved in <NUM> of n-hexane. Yellowish powder precipitated from this solution over <NUM> hours at r. was filtered to give <NUM> (<NUM>%) of <NUM>-(<NUM>-inden-<NUM>-yl)-<NUM>'-(<NUM>-inden-<NUM>-yl)biphenyl as a mixture of isomers.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM> and <NUM> (<NUM>, sum <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (dd, J = <NUM>, J = <NUM>) and <NUM> (dd, J = <NUM>, J = <NUM>) {sum <NUM>}, <NUM> (d, J = <NUM>, <NUM>), <NUM> and <NUM> (<NUM>, sum <NUM>), <NUM> (s, <NUM>), <NUM> (dd, J = <NUM>, J = <NUM>) and <NUM> (dd, J = <NUM>, J = <NUM>) {sum <NUM>}, <NUM> and <NUM> (<NUM>, sum <NUM>), <NUM>-<NUM> (m, <NUM>).

To a white suspension of <NUM> (<NUM> mmol) of <NUM>,<NUM>'-(<NUM>H-inden-<NUM>-yl)(<NUM>H-inden-<NUM>-yl)biphenyl (L135) in <NUM> of ether <NUM> (<NUM> mmol) of <NUM> n-butyllithium in hexanes were added in one portion at -<NUM>. This mixture was stirred overnight at r. , then the resulting yellow solution with a lot of yellow precipitate was cooled to -<NUM>, and <NUM> (<NUM> mmol) of ZrCl<NUM> was added. The reaction mixture was stirred overnight at r. to give orange solution with orange precipitate. This mixture was evaporated to dryness. The residue was heated with <NUM> of toluene, and the suspension formed was filtered while hot through glass frit (G4). <NUM> (<NUM>%) of the title compound were separated from the resulting filtrate by fractional crystallization.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>).

NaOH (<NUM>, <NUM> mmol, <NUM> equiv. ) was dissolved in a mixture of <NUM> of EtOH and <NUM> of water. The solution was cooled to r. , and propiophenone (<NUM>, <NUM> mmol, <NUM> equiv. ) was added in one portion. Then, <NUM>-bromobenzaldehyde (<NUM>, <NUM> mmol, <NUM> equiv) was added in one portion, and the resulting mixture was stirred at r. overnight and then for <NUM> at <NUM>. The reaction mixture was poured into <NUM> of water and extracted with diethyl ether (<NUM>×<NUM>). The combined organic extract was dried over Na<NUM>SO<NUM>, and the solvents were removed in vacuum. The residue was distilled in vacuum, and fraction with b. <NUM>-<NUM>/<NUM> mbar was collected. It contained ca. <NUM> mol% of propiophenone according to <NUM>H NMR spectrum. This procedure afforded <NUM> (<NUM>%) of the title compound as greenish oil which was used without further purification.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (br. s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>).

<NUM>-(<NUM>-Bromophenyl)-<NUM>-methyl-<NUM>-phenylprop-<NUM>-ene-<NUM>-one (<NUM>, <NUM> mmol) was added in one portion to the polyphosphoric acid (prepared from <NUM> of <NUM>% phosphoric acid and <NUM> of P<NUM>O<NUM>). The mixture was stirred at <NUM> for <NUM>, then cooled to ambient temperature, and poured into <NUM> of water. The crude product was extracted with diethyl ether (<NUM>×<NUM>). The combined organic extract was dried over Na<NUM>SO<NUM> and then evaporated to dryness. The remaining propiophenone and all other volatiles were removed in high vacuum using Kugelrohr apparatus. This procedure afforded <NUM> (<NUM>%) of the title compound as red oil. The product was a mixture of two diastereomers, A and B, in molar ratio ~ <NUM>:<NUM> according to <NUM>H NMR spectrum.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ (<NUM>, d, <NUM> in B, J = <NUM>), <NUM> (d, <NUM> in A, J = <NUM>), <NUM>-<NUM> (m, <NUM> in A and B), <NUM>-<NUM> (m, <NUM> in A), <NUM> (dd, <NUM> in B, J = <NUM>, J = <NUM>), <NUM> (dd, <NUM> in B, J = <NUM>), <NUM>-<NUM> (m, <NUM> in A), <NUM> (quint, <NUM> in B, J = <NUM>), <NUM>-<NUM> (m, <NUM> in B), <NUM> (d, <NUM> in A, J = <NUM>), <NUM> (d, <NUM> in B, J = <NUM>).

<NUM>-(<NUM>-Bromophenyl)-<NUM>-methyl-<NUM>,<NUM>-dihydro-<NUM>-inden-<NUM>-one (<NUM>, <NUM> mmol) was dissolved in a mixture of <NUM> of THF and <NUM> of methanol. NaBH<NUM> (<NUM>, <NUM> mmol, <NUM> equiv. ) was added in small portions to this solution. After completion of addition the reaction mixture was stirred overnight at r. and then poured into <NUM> of water. The product was extracted with diethyl ether (<NUM>×<NUM>). The combined organic extract was washed with water, dried over Na<NUM>SO<NUM> and then evaporated to dryness. The residue was dissolved in <NUM> of toluene, and catalytic amount of TsOH was added. The resulting mixture was refluxed using Dean-Stark apparatus for <NUM>, then cooled to r. and passed through a short pad of silica gel <NUM> (<NUM>-<NUM>). The solution was evaporated to dryness, the residue was dissolved in hexane, and the solution was passed through a short pad of silica gel. The resulting solution was evaporated to dryness. This procedure afforded <NUM> (<NUM>%) of the title compound as white solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (br.

A mixture of <NUM>-(<NUM>-bromophenyl)-<NUM>-methyl-<NUM>-indene (<NUM>, <NUM> mmol, <NUM> equiv. ), <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-(<NUM>-phenyl-<NUM>H-indene-<NUM>-yl)-<NUM>,<NUM>,<NUM>-dioxaborolane (<NUM>, <NUM> mmol, <NUM> equiv. ), Na<NUM>CO<NUM> (<NUM>, <NUM> mmol, <NUM> equiv), toluene (<NUM>), ethanol (<NUM>), and water (<NUM>) was placed in a heavy wall glass pressure vessel. Argon was bubbled through the mixture for <NUM>, and then Pd(PPh<NUM>)<NUM> (<NUM>, <NUM> mmol, <NUM> equiv. ) was added. The resulting mixture was stirred overnight at <NUM>, cooled to r. , diluted with water, and the crude product was extracted with toluene (<NUM>×<NUM>). The combined organic extract was washed with water, dried over Na<NUM>SO<NUM>, and then evaporated to dryness. The residue was dissolved in hexane, and the obtained solution was passed through a short pad of silica gel <NUM> (<NUM>-<NUM>). The solvent was evaporated, and the residue was recrystallized from hexane. This procedure afforded <NUM> (<NUM>%) of the title compound as an off-white solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (s, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (br. s, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>).

Isovaleroyl chloride (<NUM>, <NUM> mmol, <NUM> equiv) was added dropwise to the suspension of AlCl<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) in dry benzene (<NUM>) at <NUM>. The cooling bath was removed and the reaction mixture was allowed to warm to r. and then stirred for <NUM>. Then the reaction mixture was poured onto crushed ice, the organic layer was separated and the aqueous layer was extracted with benzene (<NUM>×<NUM>). The combined organic extracts were dried over Na<NUM>SO<NUM> and evaporated to dryness. The residue was distilled and fraction with b. <NUM>/<NUM> mbar was collected. This procedure gave <NUM> (<NUM>%) of the product as colorless oil.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>).

n-Butyllithium (<NUM>, <NUM> mmol, <NUM> equiv) was added dropwise to a solution of N,N-diisopropylamine (<NUM>, <NUM> mmol, <NUM> equiv) in dry THF (<NUM>) at -<NUM>. The resulting mixture was stirred for <NUM>. A solution of <NUM>-methyl-<NUM>-phenylbutan-<NUM>-one (<NUM>, <NUM> mmol, <NUM> equiv) in dry THF (<NUM>) was added dropwise to the mixture at the same temperature. The resulting mixture was stirred for <NUM> and a solution of <NUM>-bromobenzaldehyde (<NUM>, <NUM> mmol, <NUM> equiv) in dry THF (<NUM>) was added dropwise. The resulting mixture was stirred for <NUM> and the solution of <NUM> HCl (<NUM>, <NUM> mmol, <NUM> equiv) in <NUM> of MeOH was added at -<NUM>. The reaction mixture was allowed to warm to r. , stirred for <NUM>, and then poured into water. The mixture was extracted with ether (<NUM>×<NUM>), the combined organic extracts were dried over Na<NUM>SO<NUM> and evaporated to dryness. All volatiles were removed from the residue under high vacuum using Kugelrohr apparatus to afford the title product (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (dd, <NUM>, J = <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (td, <NUM>, J = <NUM>, J = <NUM>), <NUM> (dd, <NUM>, J = <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (dd, <NUM>, J = <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

Triethylamine (<NUM>, <NUM> mmol, <NUM> equiv) was added to a solution of <NUM>-((<NUM>-bromophenyl)(hydroxy)methyl)-<NUM>-methyl-<NUM>-phenylbutan-<NUM>-one (<NUM>, <NUM> mmol, <NUM> equiv), in <NUM> of dry THF at <NUM>. A solution of methanesulfonyl chloride (<NUM>, <NUM> mmol, <NUM> equiv) in <NUM> of dry THF was added dropwise at the same temperature and the reaction mixture was stired overnight. The mixture was poured into water and the crude product was extracted with ether (<NUM>×<NUM>), the combined organic extracts were dried over Na<NUM>SO<NUM> and evaporated to dryness. The resulting solid was washed with methanol to afford the title product as white powder (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (br. s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (br. s, <NUM>), <NUM> (br. s, <NUM>), <NUM> (s, <NUM>), <NUM> (br. s, <NUM>), <NUM> (d, <NUM>, J = <NUM>).

<NUM>-Benzoyl-<NUM>-(<NUM>-bromophenyl)-<NUM>-methylbutyl methanesulfonate (<NUM>, <NUM> mmol, <NUM> equiv) and DBU (<NUM>, <NUM> mmol, <NUM> equiv. ) were mixed in <NUM> of dry THF and the resulting mixture was stirred overnight at <NUM>. The mixture was poured into water and the crude product was extracted with ether (<NUM>×<NUM>), the combined organic extracts were dried over Na<NUM>SO<NUM> and evaporated to dryness to afford the title product as yellow oil (<NUM>, <NUM>%).

<NUM>H NMR (<NUM>, CDCl<NUM>, mixture of <NUM> isomers): δ <NUM>-<NUM> (m), <NUM>-<NUM> (m), <NUM> (d), <NUM> (t), <NUM> (t), <NUM>-<NUM> (m), <NUM>-<NUM> (m), <NUM> (s), <NUM>-<NUM> (m), <NUM>-<NUM> (m).

<NUM>-(<NUM>-Bromobenzylidene)-<NUM>-methyl-<NUM>-phenylbutan-<NUM>-one (<NUM>) was added in one portion to polyphosphoric acid (prepared from <NUM> of <NUM>% phosphoric acid and <NUM> of P<NUM>O<NUM>). The mixture was stirred at <NUM> for <NUM>, then cooled to ambient temperature, and poured into <NUM> of water. The crude product was extracted with diethyl ether (<NUM>×<NUM>). The combined organic extract was dried over Na<NUM>SO<NUM> and then evaporated to dryness. All other volatiles were removed in high vacuum using Kugelrohr apparatus. This procedure afforded <NUM> (<NUM>%) of the title compound as red oil.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (br. s, <NUM>), <NUM> (br. s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>).

<NUM>-(<NUM>-Bromophenyl)-<NUM>-isopropyl-<NUM>,<NUM>-dihydro-<NUM>-inden-<NUM>-one (<NUM>, <NUM> mmol, <NUM> equiv) was dissolved in a mixture of <NUM> of THF and <NUM> of methanol. NaBH<NUM> (<NUM>, <NUM> mmol, <NUM> equiv. ) was added in small portions to this solution. After that, the reaction mixture was stirred overnight at r. and then poured into <NUM> of water. The product was extracted with diethyl ether (<NUM>×<NUM>). The combined organic extract was washed with water, dried over Na<NUM>SO<NUM> and then evaporated to dryness. The residue was dissolved in <NUM> of toluene, and a catalytic amount of TsOH was added. The resulting mixture was refluxed using Dean-Stark apparatus for <NUM>, then cooled to r. and passed through a short pad of silica gel <NUM> (<NUM>-<NUM>). The filtrate was evaporated to dryness, the residue was dissolved in hexane, and the solution obtained was passed through a short pad of silica gel. The resulting solution was evaporated to dryness. This procedure afforded <NUM> (<NUM>%) of the title compound as white solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

A mixture of <NUM>-(<NUM>-bromophenyl)-<NUM>-isopropyl-<NUM>H-indene (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>-(<NUM>H-inden-<NUM>-yl)-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM>-dioxaborolane (<NUM>, <NUM> mmol, <NUM> equiv), sodium carbonate (<NUM>, <NUM> mmol, <NUM> equiv), tetrakis(triphenylphosphine)palladium (<NUM>, <NUM> mmol, <NUM> equiv), <NUM> of toluene, <NUM> of ethanol and <NUM> of water was stirred at <NUM> overnight. After cooling to r. , water (<NUM>) was added and the mixture was extracted with ethyl acetate (<NUM>×<NUM>). The combined extracts were dried over Na<NUM>SO<NUM> and evaporated in vacuum. Column chromatography on silica gel <NUM> (<NUM>-<NUM>, eluent: hexane/dichloromethane = <NUM>:<NUM>, vol. ) afforded <NUM> (<NUM>%) of the title product as a yellowish solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (AB quartet, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

A mixture of <NUM>-(<NUM>-bromophenyl)-<NUM>-isopropyl-<NUM>H-indene (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>-(<NUM>,<NUM>-dimethyl-<NUM>H-inden-<NUM>-yl)-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM>-dioxaborolane (<NUM>, <NUM> mmol, <NUM> equiv), sodium carbonate (<NUM>, <NUM> mmol, <NUM> equiv),
tetrakis(triphenylphosphine)palladium (<NUM>, <NUM> mmol, <NUM> equiv), <NUM> of toluene, <NUM> of ethanol and <NUM> of water was stirred at <NUM> overnight. After cooling to r. , water (<NUM>) was added and the mixture was extracted with ethyl acetate (<NUM>×<NUM>). The combined extracts were dried over Na<NUM>SO<NUM> and evaporated in vacuum. Column chromatography on silica gel <NUM> (<NUM>-<NUM>, eluent: hexane/dichloromethane = <NUM>:<NUM>, vol. ) afforded <NUM> (<NUM>%) of the title product as a yellowish solid.

<NUM>H NMR (<NUM>, CDCl<NUM>, mixture of <NUM> isomers): δ <NUM>-<NUM> (m), <NUM> (s), <NUM> (s), <NUM> (d), <NUM> (s), <NUM> (d), <NUM> (s), <NUM> (s), <NUM>-<NUM> (m), <NUM>-<NUM> (m), <NUM> (s), <NUM> (s), <NUM> (d), <NUM> (d), <NUM>-<NUM> (m), <NUM> (d).

A mixture of <NUM>-(<NUM>-bromophenyl)-<NUM>-isopropyl-<NUM>H-indene (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-(<NUM>-phenyl-<NUM>H-inden-<NUM>-yl)-<NUM>,<NUM>,<NUM>-dioxaborolane (<NUM>, <NUM> mmol, <NUM> equiv), sodium carbonate (<NUM>, <NUM> mmol, <NUM> equiv),
tetrakis(triphenylphosphine)palladium (<NUM>, <NUM> mmol, <NUM> equiv), <NUM> of toluene, <NUM> of ethanol and <NUM> of water was stirred at <NUM> overnight. After cooling to r. , water (<NUM>) was added and the mixture was extracted with ethyl acetate (<NUM>×<NUM>). The combined extracts were dried over Na<NUM>SO<NUM> and evaporated in vacuum. Column chromatography on silica gel <NUM> (<NUM>-<NUM>, eluent: hexane/dichloromethane = <NUM>:<NUM>, vol,) afforded <NUM> (<NUM>%) of the title product as a yellowish solid.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, <NUM>, J = <NUM>), <NUM> (td, <NUM>, J = <NUM>, J = <NUM>), <NUM> (td, <NUM>, J = <NUM>, J = <NUM>), <NUM> (s, <NUM>), <NUM> (dd, <NUM>, J = <NUM>, J = <NUM>), <NUM> (br. s, <NUM>), <NUM> (s, <NUM>), <NUM> (AB quartet, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

PdCl<NUM> (<NUM>, <NUM> mmol, <NUM> equiv. ) and PPh<NUM> (<NUM>, <NUM> mmol, <NUM> equiv. ) were added to <NUM> of dry THF, and the mixture was stirred overnight at <NUM>. <NUM>-(<NUM>-Bromophenyl)-<NUM>-methyl-<NUM>H-indene (<NUM>, <NUM> mmol, <NUM> equiv. ), bis(pinacolato)diboron (<NUM>, <NUM> mmol, <NUM> equiv. ), and KOAc (<NUM>, <NUM> mmol, <NUM> equiv. ) were added therein, and the resulting mixture was stirred at <NUM> overnight and then poured into <NUM> of water. The product was extracted with ether (<NUM>×<NUM>). The combined organic extract was dried over Na<NUM>SO<NUM> and evaporated to dryness. Purification of the residue by flash chromatography on silica gel <NUM> (<NUM>-<NUM>, eluent: hexane/dichloromethane = <NUM>:<NUM>, vol. ) afforded <NUM> (<NUM>%) of the title compound as yellow oil.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (td, <NUM>, J = <NUM>, J = <NUM>), <NUM> (br. s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

A mixture of <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-(<NUM>-(<NUM>-methyl-<NUM>H-inden-<NUM>-yl)phenyl)-<NUM>,<NUM>,<NUM>-dioxaborolane (<NUM>, <NUM> mmol, <NUM> equiv), <NUM>-bromo-<NUM>,<NUM>-diphenyl-<NUM>H-indene [synthesized as described in <CIT>] (<NUM>, <NUM> mmol, <NUM> equiv), cesium carbonate (<NUM>, <NUM> mmol, <NUM> equiv), tetrakis(triphenylphosphine)palladium (<NUM>, <NUM> mmol, <NUM> equiv) and <NUM> of dry dioxane was stirred at <NUM> overnight. After cooling to r. , water (<NUM>) was added and the mixture was extracted with ethyl acetate (<NUM>×<NUM>). The combined extracts were dried over Na<NUM>SO<NUM> and evaporated in vacuum. Column chromatography on silica gel <NUM> (<NUM>-<NUM>, eluent: hexane/dichloromethane = <NUM>:<NUM>, vol. ) afforded <NUM> (<NUM>%) of the title product as a yellowish solid.

<NUM>H NMR (<NUM>, CDCl<NUM>, mixture of isomers): δ <NUM>-<NUM> (m), <NUM>-<NUM> (m), <NUM> (d), <NUM> (d), <NUM> (d), <NUM> (s), <NUM> (s), <NUM>-<NUM> (m), <NUM> (s), <NUM> (s).

To a solution of a bridged ligand (<NUM> equiv) in dry THF (<NUM>/mmol), n-butyllithium (<NUM> equiv) was added dropwise at -<NUM> and the mixture was stirred at r. Then, Zr(NMe<NUM>)<NUM>Cl<NUM>(THF)<NUM> (<NUM> equiv) was added at -<NUM> and the resulting mixture was allowed to warm slowly to r. and then stirred overnight. The mixture was evaporated to dryness, the residue was taken up in toluene (<NUM>/mmol), and the obtained mixture was evaporated to dryness to remove traces of THF. The residue was dissolved in toluene (<NUM>/mmol), the resulting solution was filtered through a pad of Celite <NUM>. The filtrate was placed into a glass heavy wall pressure vessel and Me<NUM>SiCl<NUM> (<NUM> equiv) was added in one portion. The resulting mixture was stirred at <NUM> for <NUM>. After cooling to r. , the mixture was filtered through a pad of Celite <NUM> and the filtrate was evaporated to dryness. The residue was purified by recrystallization.

According to the General procedure A, <NUM> (<NUM>%) of the title compound (pure single isomer, syn-orientation of the methyl and phenyl groups) were obtained from <NUM>-methyl-<NUM>-(<NUM>-(<NUM>-phenyl-<NUM>H-inden-<NUM>-yl)phenyl)-<NUM>H-indene, (L140; <NUM>, <NUM> mmol, <NUM> equiv), n-butyllithium (<NUM>, <NUM> mmol, <NUM> equiv), Zr(NMe<NUM>)<NUM>Cl<NUM>(THF)<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) and Me<NUM>SiCl<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) after isolation of the crude product by recrystallization as follows. The crude product was dissolved in <NUM> of toluene, and <NUM> of hexane were added. The mixture was then filtered, and the filtrate was evaporated in vacuum to dryness. The residue was redissolved in <NUM> of toluene, and <NUM> of hexane was added. The precipitate formed was filtered and redissolved in <NUM> of hot toluene. The obtained solution was left overnight at r. , then filtered, and the filtrate was evaporated in vacuum until formation of precipitate started (~<NUM>). The mixture was left overnight at r. , the precipitate formed was filtered, washed with toluene and dried in vacuum. Thus, the first crop of the product was obtained. The filtrate was concentrated in vacuum to ~<NUM> and left overnight. The precipitate formed was filtered, washed with toluene and dried in vacuum to give the second crop of the product. The two crops were combined and dried in vacuum for <NUM> at <NUM>. The product contained <NUM> equiv. of toluene according to <NUM>H NMR spectrum.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, <NUM>, J = <NUM>), <NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (td, <NUM>, J = <NUM>, J = <NUM>), <NUM>-<NUM> (d, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM> + <NUM> in toluene), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM> in toluene) <NUM> (s, <NUM>).

According to the General procedure A, <NUM> (<NUM>%) of the title compound were obtained from <NUM>-(<NUM>-(<NUM>H-inden-<NUM>-yl)phenyl)-<NUM>-isopropyl-<NUM>H-indene, (L157; <NUM>, <NUM> mmol, <NUM> equiv), n-butyllithium (<NUM>, <NUM> mmol, <NUM> equiv), Zr(NMe<NUM>)<NUM>Cl<NUM>(THF)<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) and Me<NUM>SiCl<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) after recrystallization of the crude product from <NUM> of toluene.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM> (dd, <NUM>, J = <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

According to the General procedure A, <NUM> (<NUM>%) of the title compound were obtained from <NUM>-(<NUM>-(<NUM>-isopropyl-<NUM>H-inden-<NUM>-yl)phenyl)-<NUM>,<NUM>-dimethyl-<NUM>H-indene (L158; <NUM>, <NUM> mmol, <NUM> equiv), n-butyllithium (<NUM>, <NUM> mmol, <NUM> equiv), Zr(NMe<NUM>)<NUM>Cl<NUM>(THF)<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) and Me<NUM>SiCl<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) after recrystallization of the crude product from <NUM> of toluene.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (dd, <NUM>, J = <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

According to the General procedure A, <NUM> (<NUM>%) of the title compound were obtained as <NUM>:<NUM> mixture of two isomers from <NUM>-isopropyl-<NUM>-(<NUM>-(<NUM>-phenyl-<NUM>H-inden-<NUM>-yl)phenyl)-<NUM>H-indene (L179; <NUM>, <NUM> mmol, <NUM> equiv), n-butyllithium (<NUM>, <NUM> mmol, <NUM> equiv), Zr(NMe<NUM>)<NUM>Cl<NUM>(THF)<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) and Me<NUM>SiCl<NUM> (<NUM>, <NUM> mmol, <NUM> equiv). Separation of isomers was conducted as follows: a portion (<NUM>) of <NUM>:<NUM> mixture of isomers was recrystallized from <NUM> hexane-dichloromethane mixture (<NUM>:<NUM>, vol. ) to afford <NUM> of pure isomer <NUM> (syn-orientation of the isopropyl and phenyl groups). The mother liquor was evaporated to <NUM> and the precipitate was filtered off (a mixture of isomers according to <NUM>H NMR). The filtrate was evaporated to dryness and the resulting solid was recrystallized from <NUM> of hexane to afford <NUM> of pure isomer <NUM> (anti-orientation of the isopropyl and phenyl groups).

<NUM>H NMR (<NUM>, CDCl<NUM>, isomer <NUM>): δ <NUM> (dd, <NUM>, J = <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (td, <NUM>, J = <NUM>, J = <NUM>), <NUM> (td, <NUM>, J = <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

<NUM>H NMR (<NUM>, CDCl<NUM>, isomer <NUM>): δ <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>).

According to the General procedure A, <NUM> (<NUM>%) of the title compound were obtained from <NUM>-(<NUM>-(<NUM>-methyl-<NUM>H-inden-<NUM>-yl)phenyl)-<NUM>,<NUM>-diphenyl-<NUM>H-indene (L182; <NUM>, <NUM> mmol, <NUM> equiv), n-butyllithium (<NUM>, <NUM> mmol, <NUM> equiv), Zr(NMe<NUM>)<NUM>Cl<NUM>(THF)<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) and Me<NUM>SiCl<NUM> (<NUM>, <NUM> mmol, <NUM> equiv) after recrystallization of the crude product from <NUM> of toluene and washing the resulting crystals with diethyl ether.

<NUM>H NMR (<NUM>, CDCl<NUM>): δ <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J= <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, <NUM>, J = <NUM>), <NUM> (s, <NUM>).

The polymerisations were carried out in a PPR48 Parallel Pressure Reactor (PPR) for olefin polymerisation. This equipment, containing <NUM> reactors mounted in a triple glove-box, was sold commercially by the company Symyx, thereafter by the company Freeslate. The applied polymerisation protocols were as follows:.

Prior to the execution of a library, the <NUM> PPR cells (reactors) undergo 'bake-and-purge' cycles overnight (<NUM> at <NUM>-<NUM> with intermittent dry N2 flow), to remove any contaminants and left-overs from previous experiments. After cooling to glove-box temperature, the stir tops are taken off, and the cells are fitted with disposable <NUM> glass inserts and PEEK stirring paddles (previously hot-dried under vacuum); the stir tops are then set back in place, the cells are loaded with the proper amounts of toluene (in the range <NUM>-<NUM>), <NUM>-hexene (in the range <NUM> -<NUM>) and MAO solution (<NUM>µL of <NUM> mol L-<NUM> in toluene), thermostated at <NUM>, and brought to the operating pressure of <NUM> kPa (<NUM> psig) with ethylene. At this point, the catalyst injection sequence is started; proper volumes of a toluene 'chaser', a solution of the precatalyst in toluene (typically in the range <NUM>-<NUM> mmol L-<NUM>), and a toluene 'buffer' are uptaken into the slurry needle, and then injected into the cell of destination. The reaction is left to proceed under stirring (<NUM> rpm) at constant temperature and pressure with continuous feed of ethylene for <NUM>-<NUM>, and quenched by over-pressurizing the cell with dry air (preferred to other possible catalyst poisons because in case of cell or quench line leaks oxygen is promptly detected by the dedicated glove-box sensor).

After quenching, the cells are cooled down and vented, the stir-tops are removed, and the glass inserts containing the reaction phase are taken out and transferred to a Genevac EZ2-Plus centrifugal evaporator, where all volatiles are distilled out and the polymers are thoroughly dried overnight. Reaction yields are double-checked against on-line monomer conversion measurements by robotically weighing the dry polymers in a Bohdan Balance Automator while still in the reaction vials (subtracting the pre-recorded tare). Polymer aliquots are then sampled out for the characterizations.

GPC curves are recorded with a Freeslate Rapid GPC setup, equipped with a set of <NUM> mixed-bed Agilent PLgel <NUM> columns and a Polymer Char IR4 detector. The upper deck of the setup features a sample dissolution station for up to <NUM> samples in <NUM> magnetically stirred glass vials, <NUM> thermostated bays each accommodating <NUM> polymer solutions in <NUM> glass vials, and a dual arm robot with two heated injection needles. With robotic operation, preweighed polymer amounts (typically <NUM>-<NUM>) are dissolved in proper volumes of orthodichlorobenzene (ODCB) containing <NUM> mL-<NUM> of <NUM>-methyl-<NUM>,<NUM>-di-tert-butylphenol (BHT) as a stabilizer, so as to obtain solutions at a concentration of <NUM> to <NUM> mL-<NUM>. After <NUM>-<NUM> at <NUM> under gentle stirring to ensure complete dissolution, the samples are transferred to a thermostated bay at <NUM>, and sequentially injected into the system at <NUM> and a flow rate of <NUM> min-<NUM>. In post-trigger delay operation mode, the analysis time is <NUM> per sample. Calibration is carried out with the universal method, using <NUM> monodisperse polystyrene samples (Mn between <NUM> and <NUM> KDa). Before and after each campaign, samples from a known i-PP batch produced with an ansa-zirconocene catalyst are analyzed for a consistency check.

13C NMR spectra are recorded with a Bruker Avance <NUM> III spectrometer equipped with a <NUM> High Temperature Cryoprobe, and a robotic sample changer with pre-heated carousel (<NUM> positions). The samples (<NUM>-<NUM>) are dissolved at <NUM> in tetrachloroethane-<NUM>,<NUM>-d2 (<NUM>), added with <NUM> mL-<NUM> of BHT as a stabilizer, and loaded in the carousel maintained at the same temperature. The spectra are taken sequentially with automated tuning, matching and shimming. Typical operating conditions for routine measurements are: <NUM>° pulse; acquisition time, <NUM>; relaxation delay, <NUM>; <NUM>-<NUM> transients (corresponding to an analysis time of <NUM>-<NUM>). Broad-band proton decoupling is achieved with a modified WALTZ16 sequence (BI_WALTZ16_32 by Bruker).

The catalyst activity is indicated by Rp, the calculated polymerisation rate, expressed as kilograms of copolymer, produced per mmol of catalyst per mol of ethylene in the reactor-diluent per hour [kg / (mmolcat·[C<NUM>H<NUM>]·h)].

The hexene (C6) reactivity (in mol%/vol%) is expressed as mol percent hexene-incorporation in the copolymer (C6 inc. , in mol%) per volume percent <NUM>-hexene in the reaction diluent (C6, in vol%). This reactivity is the averaged value of the polymerisation runs. Obviously, a higher hexene-incorporation per volume percent in the reaction-medium indicates a higher hexene reactivity.

The weight average molecular weight is expressed in kiloDaltons (kDa).

The catalysts that were employed in the PPR polymerisation experiments are presented in table <NUM> below.

The experimental results are summarized in Table <NUM>.

Experiment A is comparative and reflects example III. <NUM> of <CIT>; Experiment B also is comparative and reflects example VIII. <NUM> of <CIT>; Experiment C also is comparative. Experiments D through H are experiments according to the present invention.

Claim 1:
Metallocene complex according to formula I,
<CHM>
wherein R<NUM> and R<NUM> are independently selected from H, an alkyl or an aryl group, wherein R<NUM> is a C1-C10 alkyl group, wherein R' is selected from H, an alkyl group, an aryl group and wherein different R' substituents can be connected to form a ring structure,
and wherein B is a <NUM>,<NUM> phenylene bridging moiety or a substituted <NUM>,<NUM>-phenylene bridging moiety substituted on the <NUM>, <NUM>, <NUM> or <NUM> position with alkyl or aryl groups,
wherein Mt is selected from Ti, Zr and Hf, X is an anionic ligand, z is the number of X groups and equals the valence of Mt minus <NUM>.