Metallocenes for the manufacture of polypropylene

Abstract

The disclosure relates to a metallocene complex of formula (I) wherein Mt is Zr or Hf; X is a sigma ligand; R1 are each independently, same or different from each other, C1-C20 hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8 ring; R2 and R2' are each independently, same or different from each other, CH2-R21, with R21 being H, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or a C6-C9-aryl, provided that R2 and R2' are not both methyl; R3 and R4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20 aryl, or -OR31, with R31 being C1-C10-hydrocarbyl, whereby at least one R3 per phenyl group and at least one R4 is not H; R5 and R6 are each independently, same or different from each other, C1-C10 hydrocarbyl, or may form together with the C atoms they are attached to a C5-C7 carbocycle; R51' is C1-C10-hydrocarbyl; and R6' is C(R61)3, with R61 being linear or branched C1-C6-alkyl.

Description

[0001] METALLOCENES FOR THE MANUFACTURE OF POLYPROPYLENE FIELD OF THE DISCLOSURE The present disclosure relates to new bisindenyl ligands, complexes thereof, and catalysts comprising those complexes. The present disclosure also relates to the use of the new bisindenyl metallocene catalysts for the production of polypropylene homopolymers or propylene copolymers, especially with ethylene, in particular heterophasic polypropylene, with high activity levels, high molecular weight, and hence low MFR, and with ideal melting points. The catalysts are especially useful in the manufacture of propylene ethylene copolymers as they exhibit remarkable catalyst activity in such polymerizations. BACKGROUND OF THE DISCLOSURE Metallocene catalysts have been used to manufacture polyolefins for many years. Countless academic and patent publications describe the use of these catalysts in olefin polymerization. Metallocenes are now used industrially and polyethylenes and polypropylenes in particular are often produced using cyclopentadienyl-based catalyst systems with different substitution patterns. WO2019179959 describes C1-symmetric bisindenyl complexes comprising indenyl moiety bearing 5-methoxy substituents and 6-tert-butyl substituents and an indacenyl moiety. The catalysts provide somewhat high Tm of hPP varying from 154 to 156 °C in the presence of borate containing cocatalyst. While these prior art catalyst have their advantages, they lack in isoselectivity, in particular in the absence of borate containing cocatalyst, generating hPP with a relatively low melting and crystallisation temperature due to the formation of insertion regiodefects in the PP chains. The present inventors thus sought new metallocenes, which are able to provide high isoselectivity without compromising productivity, especially in the case of the homopolymerization of propylene or in the case of copolymerization between propylene and ethylene. The desired catalysts should also have improved performance in the production of high melting temperature and high molecular weight polypropylene homopolymers (hPP). The desired catalysts should also have improved performance in the production of propylene-ethylene copolymers, for instance having high activity for high Mw copolymer products. The desired catalysts should also provide propylene-ethylene copolymers having high molecular weight. Further, the desired catalysts should also be able to produce hPP with Tmat least 157 °C, in particular without a need for any borate containing cocatalysts, due to regulatory concerns relating to such compounds. Also the

[0002] Sensitivity: Internal desired catalyst should be able to produce heterophasic copolymers with good productivity in gas phase in order to reach the target loop / gas phase material split, higher matrix melting point and higher viscosity of the rubber phase. BRIEF DESCRIPTION OF THE DISCLOSURE An object of the present disclosure is to provide new ligands, metallocene complexes, and hence catalysts to overcome the above problems. The object of the disclosure is achieved by ligands of formula (II), metallocene complexes of formula (I), polymerization catalyst comprising said metallocene complex of formula (I), and process for polymerization of polypropylene optionally with comonomers which are characterized by what is stated in the independent claims. The preferred embodiments of the disclosure are disclosed in the dependent claims. It was surprisingly found that specific modification of C1-symmetric metallocenes incorporating larger alkyl substituent on either one of or both 2-positions of the ligands, preferably on the 2-position of the alkoxy indenyl ligand, in combination with specific substitution of the other ligand positions provide desired properties. BRIEF DESCRIPTION OF THE DRAWINGS In the following the disclosure will be described in greater detail by means of preferred embodiments with reference to the accompanying drawings, in which Figure 1 shows the correlation between catalyst productivity in gas phase and molecular weight of the soluble fraction (amorphous phase produced in gas phase); Figure 2 shows the correlation between overall catalyst productivity in gas phase and molecular weight of the soluble fraction (amorphous phase produced in gas phase); Figure 3 shows the correlation between melting point of the heterophasic copolymer and molecular weight of the soluble fraction (amorphous phase produced in gas phase). DEFINITIONS Throughout the description, the following definitions are employed: The term “C1-C20-hydrocarbyl” includes C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C20- cycloalkyl, C3-C20-cycloalkenyl, C6-C20-aryl, C7-C20-alkylaryl, and C7-C20-arylalkyl groups or of course mixtures of these groups such as cycloalkyl substituted by alkyl. Unless otherwise stated, preferred C1-C20-hydrocarbyl groups are C1-C20-alkyl, C4-C20-cycloalkyl, C5-C20-cycloalkyl-alkyl groups, C7-C20-alkylaryl groups, C7-C20-arylalkyl groups, and C6-C20- aryl groups, especially C1-C10-alkyl groups, C6-C10-aryl groups, and C7-C12-arylalkyl

[0003] Sensitivity: Internal groups, e.g. C1-C8alkyl groups. Most especially preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl, and benzyl. The term “C1-C10-hydrocarbyl” includes C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C3-C10-cycloalkyl, C3-C10-cycloalkenyl, C6-C10-aryl, C7-C10-alkylaryl, and C7-C10-arylalkyl groups or of course mixtures of these groups such as cycloalkyl substituted by alkyl. Unless otherwise stated, preferred C1-C10-hydrocarbyl groups are C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-cycloalkyl-alkyl groups, C7-C10-alkylaryl groups, C7-C10-arylalkyl groups, and C6-C10-aryl groups, especially C1-C6-alkyl groups, C6-aryl groups, and C7-C10-arylalkyl groups, e.g. C1-C6-alkyl groups. Most especially preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl, and benzyl. It is to be noted that linear and branched hydrocarbyl groups cannot contain cyclic units. Aliphatic hydrocarbyl groups cannot contain aryl rings. The term “heteroatoms of Group 14-16 of the Periodic Table” includes for example Si, N, O or S. The term “C4-C8-ring” as used herein in connection to -R1 2Si-, refers to cyclic groups containing 4 to 8 carbon atoms and a Si atom and includes for example silacycloalkanediyls, such as silacyclobutane, silacyclopentane, or 9-silafluorene. The term “halogen” includes fluoro, chloro, bromo, and iodo groups, especially chloro or fluoro groups, when relating to the complex definition. The oxidation state of the metal ion is governed primarily by the nature of the metal ion in question and the stability of the individual oxidation states of each metal ion. It is appreciated that in the complexes of the invention, the metal ion is coordinated by ligands X to satisfy the valence of the metal ion and to fill its available coordination sites. The nature of these sigma-ligands can vary greatly. The numbering of these rings will be evident from the structures indicated herein. Catalyst activity is defined in this application to be the amount of polymer produced / g catalyst / h. Catalyst metal activity is defined here to be the amount of polymer produced / g Metal / h. The term productivity is also sometimes used to indicate the catalyst activity although herein it designates the amount of polymer produced per unit weight of catalyst. The term “molecular weight” is used herein to refer to weight average molecular weight Mw unless otherwise stated.

[0004] Sensitivity: Internal The term “consisting essentially of” is used herein to refer to that further components may be present namely those not materially affecting the essential characteristics of the compound or composition e.g. minor amounts of impurities. DETAILED DESCRIPTION OF THE DISCLOSURE Metallocene catalyst complexes The metallocene catalyst complexes of the invention are asymmetrical. Asymmetrical means simply that the two ligands forming the metallocene are different, that is, each ligand bears a set of substituents that are chemically different. The metallocene complexes of the invention are preferably chiral, racemic, bridged bisindenyl C1-symmetric metallocenes in their anti-configuration. Although the complexes of the invention are formally C1-symmetric, the complexes ideally retain a pseudo-C2- symmetry since they maintain C2-symmetry in close proximity of the metal center although not at the ligand periphery. By nature of their chemistry both anti and syn enantiomer pairs (in case of C1-symmetric complexes) are formed during the synthesis of the complexes. For the purpose of this invention, racemic-anti means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic-syn means that the two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the scheme below. Racemic Anti Racemic Syn Formula (I), and any sub formulae, are intended to cover both syn- and anti-configurations. Preferred metallocene catalyst complexes are in the anti-configuration. The metallocene complexes of the invention are preferably employed as the racemic-anti- isomers. Ideally, therefore at least 95% mol, such as at least 98 %mol, especially at least 99 %mol of the metallocene catalyst complex is in the racemic anti-isomeric form.

[0005] Sensitivity: Internal The present metallocene catalyst complexes require the combination of three distinctive features of the ligand framework: 1: an indenyl, preferably indacenyl, ligand with 4,8-diaryl substitution, 2: a 5-hydrocarbyloxy, preferably 5-alkoxy indenyl, preferably methoxy indene, with 6- tertiary hydrocarbyl, preferably tertiary alkyl, most preferably tert-butyl, substituent, and 3: at least one larger alkyl substituent on the 2-positions of the ligands, preferably on the 2-position of the alkoxy indenyl ligand The present invention accordingly relates to metallocene complexes of formula (I) wherein Mt is Zr or Hf; X is a sigma ligand; R1are each independently, same or different from each other, C1-C20-hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8-ring; R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl, provided that R2 and R2’ are not both methyl; R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20-aryl, or -OR31, with R31being C1-C10- hydrocarbyl,whereby at least one R3per phenyl group and at least one R4is not H; R5and R6are each independently, same or different from each other, C1-C10-hydrocarbyl, or may form together with the C atoms they are attached to a C5-C7-carbocycle;

[0006] Sensitivity: Internal R51’ is C1-C10-hydrocarbyl; and R6’ is C(R61)3, with R61being linear or branched C1-C6-alkyl. For the above-defined metallocene complexes of formula (I), the following represent preferable embodiments, which can be selected alone or in combination: In a complex of formula (I) it is preferred if Mt is Zr or Hf, preferably Zr. Each X is a sigma ligand. Preferably, each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R´ group, where R´ is C1-C6-alkyl, phenyl, or benzyl. More preferably, each X is independently, same or different from each other, Cl, benzyl, or methyl. It is preferred that both X groups are the same. Most preferably both X are Cl, methyl, or benzyl, especially Cl. Preferably R1are each independently, same or different from each other, C1-C10- hydrocarbyl, more preferably C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-cycloalkyl-alkyl, C7- C10-arylalkyl, C6-C10-aryl, or C7-C10-alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert- butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, even more preferably both are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In an embodiment each R1is independently, same or different from each other, C1-C10-alkyl, optionally substituted with C1-C10-alkoxy. It is preferred that both R1groups are the same. Most preferably, both R1are methyl. Preferably, R1are each independently, same or different from each other, C1-C6 alkyl, more preferably methyl. Preferably R2and R2’are each independently, same or different from each other, CH2-R21, with R21being H, linear C1-C6-alkyl, branched C3-C6-alkyl, or C3-C8 cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl, provided that R2and R2’ are not both methyl, more preferably R21being H, linear C1-C3-alkyl, or branched C3-alkyl, provided that R2and R2’ are not both methyl. It is preferred that R2’is not methyl, and preferably is CH2-R21, with R21being linear C1-C6-alkyl or branched C3-C6- alkyl, more preferably, R21being linear C1-C3-alkyl or branched C3-alkyl, and R2is CH2- R21, with R21being H, linear C1-C6-alkyl, or branched C3-C6-alkyl, preferably R21being H, linear C1-C6-alkyl or branched C3-alkyl. It is further preferred that R2is methyl or ethyl. Most preferably, R2is methyl or ethyl and R2’is ethyl or n-propyl. Advantageously, R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H or linear or branched C1-C6-alkyl; preferably H or linear

[0007] Sensitivity: Internal preferably H or linear C1-C6-alkyl, more preferably H or linear C1-C4alkyl; preferably H, methyl or ethyl, provided that R2and R2’ are not both methyl. In some embodiments, one of R2and R2’ is methyl, and the other is of the formula CH2- R21, with R21being linear or branched C1-C6-alkyl. In such embodiments, R21is preferably linear or branched C1-C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl. In some embodiments, R2is methyl, and R2’ is of the formula CH2-R21, with R21being linear or branched C1-C6-alkyl. In such embodiments, R21is preferably linear or branched C1- C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl. In some embodiments, neither R2nor R2’ is methyl. For example, R2and R2’is each independently, same or different from each other, CH2-R21, with R21being linear or branched C1-C6-alkyl, more preferably linear or branched C1-C4-alkyl, even more preferably methyl or ethyl, yet more preferably methyl. Preferably R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20 aryl, more preferably H, linear or branched C1-C4-alkyl, or -OR31, with R31being a C1-C4-hydrocarbyl. Even more preferably, each R3and R4are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R3per phenyl group and at least one R4is not H. Furthermore, it is possible that each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns. It is therefore preferred if one or two R3and / or R4groups is H. If two R3and / or R4groups are H then the remaining R3and / or R4group, respectively, is preferably in the para position. If one R3and / or R4group is H then the remaining R3and / or R4groups are preferably in the meta positions. Advantageously one or two R3per phenyl group are not H, more preferably on both phenyl groups the R3are the same, like 3´,5´-di-methyl or 4´- tert-butyl for both phenyl groups. For the indenyl moiety preferably one or two R4on the phenyl group are not H, more preferably two R4are not H, and most preferably these two R4are the same like 3´,5´-di- methyl or 3´,5´-di-tert-butyl.

[0008] Sensitivity: Internal In one embodiment, two R3 per phenyl group are not H and on both phenyl groups the R3 are linear or branched C1-C6-alkyl, preferably methyl, and two R4 on the phenyl group are not H and these two R4 are linear or branched C1-C6 alkyl, preferably methyl. Preferably R5and R6form together -(R56)m-, wherein each R56is independently -CH2-, - CHR*-, or -C(R*)2- group, with R* being C1-C2-alkyl, preferably methyl, and m being 3 to 5, preferably 3 to 4; more preferably in -(R56)m- each R56is -CH2-, with m being 3 to 5, preferably 3 to 4, most preferably 3. Preferably R51’ is linear or branched C1-C6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C7-C10-arylalkyl, C7-C10-alkylaryl, or C6-C10-aryl, more preferably linear C1-C6-alkyl, branched C3-C6–alkyl, or C6-aryl, even more preferably linear C1-C4-alkyl, yet even more preferably methyl or ethyl, and most preferably methyl. Preferably R6’ is C(R61)3, with R61’being linear C1-C3-alkyl; more preferably methyl. Thus advantageously, R6’ is tert-butyl. Viewed from another aspect the invention provides a metallocene catalyst complex of formula (I-a) (I-a) wherein Mt is Zr or Hf; X is a sigma ligand; n is 1 to 3, such as 1, 2 or 3, preferably 3;

[0009] Sensitivity: Internal R1are each independently, same or different from each other, C1-C20-hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8-ring; R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl, provided that R2and R2’ are not both methyl; R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20-aryl, or -OR31, with R31being C1-C10- hydrocarbyl, whereby at least one R3per phenyl group and at least one R4is not H; R51’ is C1-C10-hydrocarbyl; and R6’ is C(R61)3, with R61being linear or branched C1-C6-alkyl. For the above-defined metallocene complexes of formula (I-a), the following represent preferable embodiments, which can be selected alone or in combination: In a complex of formula (I-a) it is preferred if Mt is Zr or Hf, preferably Zr. Each X is a sigma ligand. Preferably, each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R´ group, where R´ is C1-C6-alkyl, phenyl, or benzyl. More preferably, each X is independently, same or different from each other, Cl, benzyl, or methyl. It is preferred that both X groups are the same. Most preferably both X are Cl, methyl, or benzyl, especially Cl. Preferably R1are each independently, same or different from each other, C1-C10- hydrocarbyl, more preferably C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-cycloalkyl-alkyl, C7- C10-arylalkyl, C6-C10-aryl, or C7-C10-alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert- butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, even more preferably both are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In an embodiment each R1is independently, same or different from each other, C1-C10-alkyl, optionally substituted with C1-C10-alkoxy. It is preferred that both R1groups are the same. Most preferably, both R1are methyl. Preferably, R1are each independently, same or different from each other, C1-C6 alkyl, more preferably methyl. Preferably R2and R2’are each independently, same or different from each other, CH2-R21, with R21being H, linear C1-C6-alkyl, branched C3-C6-alkyl, or C3-C8cycloalkyl, such as

[0010] Sensitivity: Internal methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl, provided that R2and R2’ are not both methyl, more preferably R21being H, linear C1-C3-alkyl, or branched C3-alkyl, provided that R2and R2’ are not both methyl. It is preferred that R2’is not methyl, and preferably is CH2-R21, with R21being linear C1-C6-alkyl or branched C3-C6- alkyl, more preferably, R21being linear C1-C3-alkyl or branched C3-alkyl, and R2is CH2- R21, with R21being H, linear C1-C6-alkyl, or branched C3-C6-alkyl, preferably R21being H, linear C1-C3-alkyl, or branched C3-alkyl. It is further preferred that R2is methyl or ethyl. Most preferably, R2is methyl or ethyl and R2’is ethyl or n-propyl. Advantageously, R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H or linear or branched C1-C6-alkyl; preferably H or linear preferably H or linear C1-C6-alkyl, more preferably H or linear C1-C4alkyl; preferably H, methyl or ethyl, provided that R2and R2’ are not both methyl. In some embodiments, one of R2and R2’ is methyl, and the other is of the formula CH2- R21, with R21being linear or branched C1-C6-alkyl. In such embodiments, R21is preferably linear or branched C1-C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl. In some embodiments, R2is methyl, and R2’ is of the formula CH2-R21, with R21being linear or branched C1-C6-alkyl. In such embodiments, R21is preferably linear or branched C1- C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl. In some embodiments, neither R2nor R2’ is methyl. For example, R2and R2’is each independently, same or different from each other, CH2-R21, with R21being linear or branched C1-C6-alkyl, more preferably linear or branched C1-C4-alkyl, even more preferably methyl or ethyl, yet more preferably methyl. Preferably R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20 aryl, more preferably H, linear or branched C1-C4-alkyl, or -OR31, with R31being a C1-C4-hydrocarbyl. Even more preferably, each R3and R4are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R3per phenyl group and at least one R4is not H. Sensitivity: Internal Furthermore, it is possible that each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns. It is therefore preferred if one or two R3and / or R4groups is H. If two R3and / or R4groups are H then the remaining R3and / or R4group, respectively, is preferably in the para position. If one R3and / or R4group is H then the remaining R3and / or R4groups are preferably in the meta positions. Advantageously one or two R3per phenyl group are not H, more preferably on both phenyl groups the R3are the same, like 3´,5´-di-methyl or 4´- tert-butyl for both phenyl groups. For the indenyl moiety preferably one or two R4on the phenyl group are not H, more preferably two R4are not H, and most preferably these two R4are the same like 3´,5´-di- methyl or 3´,5´-di-tert-butyl.In one embodiment, two R3 per phenyl group are not H and on both phenyl groups the R3 are linear or branched C1-C6-alkyl, preferably methyl, and two R4 on the phenyl group are not H and these two R4 are linear or branched C1-C6 alkyl, preferably methyl. Preferably R51’ is linear or branched C1-C6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C7-C10-arylalkyl, C7-C10-alkylaryl, or C6-C10-aryl, more preferably linear C1-C6-alkyl, branched C3-C6–alkyl, or C6-aryl, even more preferably linear C1-C4-alkyl, yet even more preferably methyl or ethyl, and most preferably methyl. Preferably R6’ is C(R61)3, with R61being linear C1-C3-alkyl; more preferably methyl. Thus advantageously, R6’ is tert-butyl. Viewed from another aspect the invention provides a metallocene catalyst complex of formula (I-b) Sensitivity: Internal wherein Mt is Zr or Hf; X is a sigma ligand; R1are each independently, same or different from each other, C1-C20-hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8-ring; R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H or linear or branched C1-C6-alkyl, provided that R2and R2’ are not both methyl; R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20-aryl, or –OR31, with R31being C1-C10- hydrocarby, whereby at least one R3per phenyl group and at least one R4is not H. For the above-defined metallocene complexes of formula (I-b), the following represent preferable embodiments, which can be selected alone or in combination: In a complex of formula (I-b) it is preferred if Mt is Zr or Hf, preferably Zr. Each X is a sigma ligand. Preferably, each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R´ group, where R´ is C1-C6-alkyl, phenyl, or benzyl. More preferably, each X is independently, same or different from each other, Cl, benzyl, or methyl. It is preferred that both X groups are the same. Most preferably both X are Cl, methyl, or benzyl, especially Cl. Preferably R1are each independently, same or different from each other, C1-C10- hydrocarbyl, more preferably C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-cycloalkyl-alkyl, C7- C10-arylalkyl, C6-C10-aryl, or C7-C10-alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert- butyl, isobutyl, C3-C8-cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, even more preferably both are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl. In an embodiment each R1is independently, same or different from each other, C1-C10-alkyl, optionally substituted with C1-C10-alkoxy. It is preferred that both R1groups are the same. Most preferably, both R1are methyl. Preferably, R1are each independently, same or different from each other, C1-C6 alkyl, more preferably methyl. Preferably R2and R2’are each independently, same or different from each other, CH2-R21, with R21being H, linear C1-C3-alkyl or branched C3-alkyl, such as methyl, ethyl, n-propyl, i- Sensitivity: Internal propyl, provided that R2and R2’ are not both methyl. It is preferred that R2’is not methyl, and preferably is CH2-R21, with R21being linear C1-C3-alkyl or branched C3-alkyl, and R2is CH2-R21, with R21being H, linear C1-C3-alkyl or branched C3-alkyl. It is further preferred that R2is methyl or ethyl. Most preferably, R2is methyl or ethyl and R2’is ethyl or n-propyl. Advantageously, R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H or linear or branched C1-C6-alkyl; preferably H or linear preferably H or linear C1-C6-alkyl, more preferably H or linear C1-C4alkyl; preferably H, methyl or ethyl, provided that R2and R2’ are not both methyl. In some embodiments, one of R2and R2’ is methyl, and the other is of the formula CH2- R21, with R21being linear or branched C1-C6-alkyl. In such embodiments, R21is preferably linear or branched C1-C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl. In some embodiments, R2is methyl, and R2’ is of the formula CH2-R21, with R21being linear or branched C1-C6-alkyl. In such embodiments, R21is preferably linear or branched C1- C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl. In some embodiments, neither R2nor R2’ is methyl. For example, R2and R2’is each independently, same or different from each other, CH2-R21, with R21being linear or branched C1-C6-alkyl, more preferably linear or branched C1-C4-alkyl, even more preferably methyl or ethyl, yet more preferably methyl. Preferably R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20 aryl, more preferably H, linear or branched C1-C4-alkyl, or -OR31, with R31being C1-C4-hydrocarbyl. Even more preferably, each R3and R4are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R3per phenyl group and at least one R4is not H. Furthermore, it is possible that each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns. It is therefore preferred if one or two R3and / or R4groups is H. If two R3and / or R4groups are H then the remaining R3and / or R4group, respectively, is preferably in the para Sensitivity: Internal position. If one R3and / or R4group is H then the remaining R3and / or R4groups are preferably in the meta positions. Advantageously one or two R3per phenyl group are not H, more preferably on both phenyl groups the R3are the same, like 3´,5´-di-methyl or 4´- tert-butyl for both phenyl groups. For the indenyl moiety preferably one or two R4on the phenyl group are not H, more preferably two R4are not H, and most preferably these two R4are the same like 3´,5´-di- methyl or 3´,5´-di-tert-butyl. In one embodiment, two R3 per phenyl group are not H and on both phenyl groups the R3 are linear or branched C1-C6-alkyl, preferably methyl, and two R4 on the phenyl group are not H and these two R4 are linear or branched C1-C6 alkyl, preferably methyl. Preferred metallocene catalysts complexes are MC-IE1, MC-IE2 and MC-IE3 as described in the examples below. Intermediates Whilst the invention primarily relates to catalysts, it will be appreciated that the complexes of the invention and the ligands used to form those complexes are also new. The novel ligands of the present invention bear the combination of the distinctive features of the metallocene ligand framework: a 5-hydrocarbyloxy, preferably 5-alkoxy indenyl, preferably methoxy indene, with 6-tertiary hydrocarbyl, preferably tertiary alkyl, most preferably tert-butyl, substituent; and a larger hydrocarbyl substituent on the 2-position of the ligand. The present invention accordingly further relates to indenes of formula (II) wherein the dotted lines represent a double bond present in between carbons 1 and 2 or 2 and 3 of the indenyl ring; Sensitivity: Internal R2’ is CH2-R21, with R21being linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9- aryl; R4are each independently, same or different from each other, H, linear or branched C1- C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20-aryl, or -OR31, with R31being C1-C10- hydrocarbyl, whereby at least one R4is not H; R51’ is C1-C10-hydrocarbyl; and R6’ is C(R61)3, with R61being linear or branched C1-C6-alkyl. For the above-defined indenes of formula (II), the following represent preferable embodiments, which can be selected alone or in combination: Preferably R2’is CH2-R21, with R21linear C1-C6-alkyl or branched C3-C6-alkyl, more preferably, R21being linear C1-C3-alkyl or branched C3-alkyl. It is further preferred that R2’ is ethyl or n-propyl. Preferably R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20-aryl, more preferably H, a linear or branched C1-C4-alkyl, or -OR31, with R31being a C1-C4-hydrocarbyl. Even more preferably, each R4are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl. It is preferred that one or two R4groups is H. If two R4groups are H then the remaining R4group is preferably in the para position. If one R4group is H then the remaining R4groups are preferably in the meta positions. Preferably two R4are not H, and most preferably these two R4are the same like 3´,5´-di- methyl or 3´,5´-di-tert-butyl. Preferably R51’ is linear or branched C1-C6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C7-C10-arylalkyl, C7-C10-alkylaryl, or C6-C10-aryl, more preferably linear C1-C6-alkyl, branched C3-C6–alkyl, or C6-aryl, even more preferably linear C1-C4-alkyl, yet even more preferably methyl or ethyl, and most preferably methyl. Preferably R6’ is C(R61)3, with R61being linear C1-C3-alkyl; more preferably methyl. Thus advantageously, R6’ is tert-butyl. Viewed from a further aspect the invention provides a polymerization catalyst comprising, preferably essentially consisting of, (i) a metallocene complex of formula (I); Sensitivity: Internal (ii) a cocatalyst system comprising a cocatalyst comprising a group 13 element; and (iii) optionally a support. Cocatalyst To form active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art. Cocatalysts comprising one or more compounds of Group 13 metals, like organoaluminium, organoboron, and / or borate compounds used to activate metallocene catalysts are suitable for use in this invention. According to the present invention a cocatalyst system comprising an aluminoxane cocatalyst and optionally a boron containing cocatalyst advantageously used in combination with the above defined metallocene catalyst complex. Preferably only cocatalysts comprising aluminium, like organoaluminium compounds used to activate metallocene catalysts, are utilized in this invention. In a preferred aspect of the present invention a cocatalyst system comprising an aluminoxane cocatalyst is advantageously used in combination with the above defined metallocene catalyst complex. Thus, preferably no further cocatalysts comprising one or more compounds of Group 13 metals other than aluminium, like organoboron and / or borate compounds, used to activate metallocene catalysts are comprised in the polymerization catalyst. Suitable amounts of cocatalyst will be well known to the person skilled in the art. Preferably, the amount of cocatalyst is chosen to reach below defined molar ratios. The molar ratio of Al from the aluminoxane to the metal ion (Mt) (preferably zirconium) of the metallocene Al / Mt may be in the range 10:1 to 2000:1 mol / mol, preferably 50:1 to 1000:1, and more preferably 100:1 to 600:1 mol / mol. When a boron cocatalyst is used, the molar ratio of boron (B) to the metal ion (Mt) (preferably zirconium) of the metallocene B / Mt may be in the range 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1, especially 0.5:1 to 3:1 mol / mol. Even more preferably, the molar ratio of feed amounts of boron (B) to metal ion (Mt), preferably zirconium, of the metallocene B / Mt is from 0.5:1 to 2:1 Alumoxane cocatalyst The aluminoxane cocatalyst can be one of formula (A): Sensitivity: Internal where n is usually from 6 to 20 and R has the meaning below. Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR3, AlR2Y and Al2R3Y3where R can be, for example, C1- C10-alkyl, preferably C1-C5-alkyl, or C3-C10-cycloalkyl, C7-C12-arylalkyl or -alkylaryl and / or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C10-alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (A). The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content. Boron containing cocatalyst According to the present invention, the aluminoxane cocatalyst can be used in combination with a boron containing cocatalyst. It will be appreciated by the person skilled in the art that where boron based cocatalysts are employed, it is normal to pre-alkylate the complex by reaction thereof with an aluminium alkyl compound, such as TIBA. This procedure is well known and any suitable aluminium alkyl, e.g. Al(C1-C6 alkyl)3 can be used. Preferred aluminium alkyl compounds are triethylaluminium, tri-isobutylaluminium, tri-isohexylaluminium, tri-n-octylaluminium and tri-isooctylaluminium. Alternatively, when a borate cocatalyst is used, the metallocene complex is in its alkylated version, that is for example a dimethyl or dibenzyl metallocene complex can be used. Boron containing cocatalysts of interest include those of formula (B) BY3 (B) wherein Y is the same or different and is hydrogen, C1-C10-haloalkyl, or C6-C20-haloaryl, or fluorine, chlorine, bromine or iodine. Sensitivity: Internal Preferred examples for Y are fluorine, trifluoromethyl, unsaturated groups such as haloaryl like p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di(trifluoromethyl)phenyl. Most preferably, Y are fluorine, trifluoromethyl, aromatic fluorinated groups such as p- fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5- di(trifluoromethyl)phenyl. Preferred boron containing cocatalysts of formula (B) are trifluoroborane, tris(4- fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, and / or tris(3,4,5-trifluorophenyl)borane. Particular preference is given to tris(pentafluorophenyl)borane. However it is preferred that borates are used, i.e. compounds containing a borate anion. These compounds have formula (C): Z4B–-W+(C) wherein Z is a substituted phenyl derivative, said substituent being halo-C1-C6-alkyl or halogen; and W+is a cationic counterion. Preferably the substituents of Z are are fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated. The borate anion Z4B–is preferably a weakly-coordinating anion such as tetrakis(pentafluorophenyl)borate. Suitable cationic counterions W+are triarylcarbenium such as triphenylcarbenium or protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n- butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N- dimethylanilinium or p-nitro-N,N-dimethylanilinium. Preferred ionic compounds which can be used according to the present invention include: tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, Sensitivity: Internal N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, or ferroceniumtetrakis(pentafluorophenyl)borate. Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate, N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate. Mostly preferred are triphenylcarbeniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate. Catalyst Manufacture The metallocene catalysts can be used in supported or unsupported form. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica- alumina. The use of a silica support is preferred. The skilled person is aware of the procedures required to support a metallocene catalyst. Especially preferably the support is a porous material so that the complex may be loaded into the pores of the support, e.g. using a process analogous to those described in WO94 / 14856, WO95 / 12622 and WO2006 / 097497. The particle size is not critical but is preferably in the range 5 to 200 μm, more preferably 20 to 80 μm. The use of these supports is routine in the art. Especially preferred procedures for producing such supported catalysts are those described in WO2020 / 239598, and WO2020 / 239603. In another embodiment, no external carrier is used but the catalyst is still presented in solid particulate form. Thus, no external support material, such as inert organic or inorganic carrier, for example silica as described above is employed. Such catalysts can be prepared as described for example in WO2003 / 051934, WO2014 / 060540, and WO2019 / 179959 The particulate support material used is an inorganic porous support such as a silica, alumina or a mixed oxide such as silica-alumina, in particular silica. Sensitivity: Internal The use of a silica support is preferred. The complex may be loaded into the pores of the particulate support, e.g. using a process analogous to those described in W094 / 14856, W095 / 12622, W02006 / 097497, and EP18282666. The average particle size of the support such as silica support can be typically from 10 to 100 µm. However, it has turned out that special advantages can be obtained, if the support has an average particle size from 15 to 80 µm, preferably from 18 to 50 µm. The average pore size of the inorganic porous support such as silica support can be in the range from 10 to 100 nm and the pore volume from 1 to 3 mL / g. The pore diameter of the inorganic porous support such as silica support can be in the range from 20 to 40 nm. The surface area of the inorganic porous support such as silica support can be typically in the range from 100 to 400 m2 / g. Examples of suitable support materials are, for instance, ES757 produced and marketed by PQ Corporation, Sylopol 948 produced and marketed by Grace or SUNSPERA DM-L- 303 silica produced by AGC Si-Tech Co. Supports can be optionally calcined prior to the use in catalyst preparation in order to reach optimal silanol group content. The use of these supports is routine in the art. The catalyst can contain from 5 to 500 µmol, such as 10 to 100 µmol of transition metal of the metallocene per gram of support such as silica, and 3 to 15 mmol of Al per gram of support such as silica. The present polymerization catalyst may be produced by e.g. as described in WO2020 / 239603 or WO2020 / 239598. A polymerization catalyst containing such metallocenes may be produced by a process including the steps of P1-a) combining the porous inorganic support with a first portion of the aluminoxane cocatalyst in a hydrocarbon solvent to obtain aluminoxane cocatalyst treated support, optionally followed by thermal treatment of the aluminoxane treated support; P1-b) dissolving the metallocene complex in a hydrocarbon solvent, preferably an aromatic solvent, more preferably toluene, optionally adding a second portion of the aluminoxane cocatalyst in the hydrocarbon solvent optionally the boron containing cocatalyst wherein the amount of the first portion of the aluminoxane cocatalyst added in step a) is 75.0 to 100.0 wt% of the total amount of aluminoxane cocatalyst and the amount the second Sensitivity: Internal portion of the aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt% of the total amount of aluminoxane cocatalyst and the boron containing cocatalyst, when present, is added in an amount that a boron / M molar ratio of feed amounts in the range of 0.1 :1 to 10:1 is reached;; P1-c) adding the solution obtained in step b) to the aluminoxane cocatalyst treated support obtained in step a) and optionally P1-d) drying the so obtained supported catalyst system. In step P1-b) of the process, the components can be mixed in any order. The optional boron containing cocatalyst can be mixed with the metallocene complex dissolved in the hydrocarbon solvent and followed by addition the optional aluminoxane, or the metallocene complex dissolved in the hydrocarbon solvent can be mixed with the optional aluminoxane and a hydrocarbon followed by addition of boron containing cocatalyst and so on. In some embodiments, all components might be combined simultaneously. Only one impregnation step is used, i.e. the treated support of step a) is loaded only in one step with the metallocene. In a preferred aspect of the present invention the process comprises P2-a) combining the porous inorganic support with aluminoxane cocatalyst in a hydrocarbon solvent to obtain aluminoxane cocatalyst treated support, optionally followed by thermal treatment of the aluminoxane treated support, filtering off the hydrocarbon solvent, optionally washing with an aromatic solvent, repeating the filtration and washing steps to remove unreacted aluminium compounds; drying the final aluminoxane cocatalyst treated support; P2-b) dissolving the metallocene in a hydrocarbon solvent optionally adding a methylaluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of methylaluminoxane cocatalyst added in step a) is 75.0 to 100.0 wt% of the total amount of methylaluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt% of the total amount of methylaluminoxane cocatalyst, to obtain a metallocene solution optionally comprising aluminoxane cocatalyst; P2-c) adding the metallocene solution to the aluminoxane cocatalyst treated support obtained in step a) and optionally P2-d) drying the so obtained supported catalyst system. Sensitivity: Internal If desired, the obtained supported catalyst system may be provided as an oil slurry with a desired solid content. The solid catalyst content in the slurry may be e.g. up to 30 wt%, like up to 25 wt%. The amounts of support, aluminoxane, preferably MAO, boron containing cocatalyst and metallocene depend on the desired herein defined ratios (boron / M, Al / M, Al / SiO2, M / SiO2). Polymerization The catalysts according to the invention are suitable for the production of propylene homopolymers, propylene-ethylene copolymers or propylene C4-10 alpha olefin copolymers, in particular heterophasic polypropylene and propylene-ethylene copolymers. Accordingly, the present disclosure relates to a process for producing a propylene homopolymer, a propylene random copolymer or a heterophasic propylene copolymer using the specific catalyst system, as defined before. The ethylene content in such a propylene-ethylene polymer may vary depending on the desired properties of the polymer. Typically, ethylene content will range from 0.1 to 10 mol%. Especially, the catalysts of the present invention are used to manufacture propylene homopolymers or propylene copolymers with ethylene as comonomer and propylene copolymers with butene as a comonomer. Thus, the present invention relates to a process for the polymerization of propylene, propylene and ethylene, or propylene and a C4-10 alpha olefin in the presence of a polymerization catalyst as described herein. In an preferred aspect the present invention relates to a process for the preparation of a heterophasic polypropylene copolymer (hPP) comprising (I) polymerizing propylene in bulk in the presence of a polymerization catalyst as defined herein to form a polypropylene homopolymer matrix; (II) in the presence of said polypropylene homopolymer matrix and said polymerization catalyst and in the gas phase, polymerizing propylene and ethylene to form a heterophasic polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber. In a further aspect the present invention relates to a process for the preparation of a heterophasic polypropylene copolymer comprising (I) polymerizing propylene in bulk in the presence of polymerization catalyst as defined herein to form a polypropylene homopolymer; Sensitivity: Internal (II) in the presence of said homopolymer and said polymerization catalyst and in the gas phase, polymerizing propylene to form a polypropylene homopolymer matrix; (III) in the presence said polypropylene homopolymer matrix and said polymerization catalyst and in the gas phase, polymerizing propylene and ethylene to form a heterophasic polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber (EPR). Polymerization in the method of the invention may be effected in one or more, e.g.1, 2, or 3, polymerization reactors, using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization, or combinations thereof, like a combination of a slurry and at least one gas phase reactor. The process may also involve an in-line pre-polymerization step. This pre-polymerization step is a conventional step used routinely in polyolefin production plants and can be carried out in a continuously stirred tank reactor (CSTR) or a loop reactor, from which the prepolymerized catalyst is then transferred together with the liquid monomer(s) into the main loop reactor. Prepolymerization can be carried out at temperatures between -10 °C and 50 °C, preferably between 10 °C and 40 °C. In case of propylene polymerization in slurry reactors, like a liquid loop reactor, the reaction temperature will generally be in the range 60 to 110 °C (e.g. 60 to 90 °C), the reactor pressure will generally be in the range 5 to 80 bar -g(e.g.20 to 60 bar-g), and the residence time will generally be in the range 0.3 to 5 hours (e.g. 0.5 to 2 hours). The liquefied monomer is usually used as reaction medium. It is a particular feature of the invention that polymerization takes place at temperatures of at least 60 °C. For gas phase reactors, the reaction temperature used will generally be in the range 60 to 115 °C (e.g.70 to 110 °C), the reactor pressure will generally be in the range 10 to 30 bar- g (e.g.15 to 25 bar-g), and the residence time will generally be 0.5 to 8 hours (e.g.0.5 to 4 hours). The gas used will be the monomer optionally as mixture with a non-reactive gas such as nitrogen or propane. In addition to actual polymerization steps and reactors, the process can contain any additional polymerization steps, like a pre-polymerization step, and any further after reactor handling steps as known in the art. For solution polymerization, an aliphatic or aromatic solvent can be used to dissolve the monomer and the polymer, and the polymerization temperature will generally be in the range 80 to 200 °C (e.g.90 to 150 °C) Sensitivity: Internal Generally, the quantity of catalyst used will depend upon the nature of the catalyst, the reactor types and conditions and the properties desired for the polymer product. As is well known in the art hydrogen can be used for controlling the molecular weight of the polymer. The metallocene catalysts of the invention possess excellent catalyst activity and good comonomer response. The catalysts are also able to provide polymers of high weight average molecular weight Mw and narrow polydispersity Mw / Mn. Moreover, the random copolymerization behavior of metallocene catalysts of the invention shows a reduced tendency of chain transfer to ethylene. It is a feature of the invention that the claimed catalysts enable the formation of polypropylene with very high melting point. These features can be achieved at commercially interesting polymerization temperatures, e.g.60 °C or more, such as from 60 °C to 90 °C. The polydispersity index (Mw / Mn) of the polymers depend on the polymerization conditions in each reactor, and can be between 2.0 and 7.0. In a particular embodiment, the propylene polymers obtained using the catalysts of the invention have a narrow polydispersity index (Mw / Mn), between 2.0 and 4.0. Propylene homopolymers made by catalyst system comprising the metallocenes of the invention can be made with Mw (weight average molecular weight) values in the range of 40 to 2000 kg / mol, preferably in the range of 50 to 1500 kg / mol depending on the use and amount of hydrogen used as Mw regulating agent. The catalysts of the invention enable the formation of polypropylene homopolymers with very high melting points. In a preferred embodiment the propylene homopolymer formed by the process of the invention has a melting point of more than 157 °C, preferably more than 158 °C. Propylene homopolymers having melting points up to 160 °C, or even up to 162 °C, are possible. Propylene copolymers with ethylene or with C4-C10 alpha olefin comonomers made by the metallocenes of the invention can be made with high productivity and low solubles. The polymers made by the catalysts of the description are useful in all kinds of end articles such as pipes, films (cast, blown or BOPP films, such as for example BOPP for capacitor film), fibers (such as spun-bond and melt-blown fibers), moulded articles (e.g. injection moulded, blow moulded, rotomoulded articles), extrusion coatings and so on. The invention will now be illustrated by reference to the following non-limiting Examples. Sensitivity: Internal EXPERIMENTAL Measurement methods Al, B and Zr determination (ICP-method) In a glovebox, an aliquot of the catalyst (ca.40 mg) was weighed into glass weighting boat using analytical balance. The sample was then allowed to be exposed to air overnight while being placed in a steel secondary container equipped with an air intake. Then 5 mL of concentrated (65 %) nitric acid was used to rinse the content of the boat into the Xpress microwave oven vessel (20 mL). A sample was then subjected to a microwave-assisted digestion using MARS 6 laboratory microwave unit over 35 minutes at 150 °C. The digested sample was allowed to cool down for at least 4 h and then was transferred into a glass volumetric glass flask of 100 mL volume. Standard solutions containing 1000 mg / L Y and Rh (0.4 mL) were added. The flask was then filled up with distilled water and shaken well. The solution was filtered through 0.45 µm Nylon syringe filters and then subjected to analysis using Thermo iCAP 6300 ICP-OES and iTEVA software. The instrument was calibrated for Al, B, Hf, Mg, Ti and Zr using a blank (a solution of 5 % HNO3) and six standards of 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L and 100 mg / L of Al, B, Hf, Mg, Ti and Zr in solutions of 5 % HNO3 distilled water. However, not every calibration point was used for each wavelength. Each calibration solution contained 4 mg / L of Y and Rh standards. Al 394.401 nm was calibrated using the following calibration points: blank, 0.1 mg / L, 1 mg / L, 10 mg / L and 100 mg / L. Al 167.079 nm was calibrated as Al 394.401 nm excluding 100 mg / L and Zr 339.198 nm using the standards of blank, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L and 100 mg / L. Curvilinear fitting and 1 / concentration weighting was used for the calibration curves. Immediately before analysis the calibration was verified and adjusted (instrument reslope function) using the blank and a 10 mg / L Al, B, Hf, Mg, Ti and Zr standard which had 4 mg / L Y and Rh. A quality control sample (QC: 1 mg / L Al, Au, Be, Hg & Se; 2 mg / L Hf & Zr, 2.5 mg / L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn & V; 4 mg / L Rh & Y; 5 mg / L Ca, K, Mg, Mn, Na & Ti; 10 mg / L Cu, Pb and Zn; 25 mg / L Fe and 37.5 mg / L Ca in a solution of 5 % HNO3 in distilled water) was run to confirm the reslope for Al, B, Hf, Mg, Ti and Zr. The QC sample was also run at the end of a scheduled analysis set. The content for Zr was monitored using Zr 339.198 nm {99} line. The content of aluminium was monitored via the 167.079 nm {502} line, when Al concentration in test portion was under 2 wt % and via the 394.401 nm {85} line for Al concentrations above 2 wt%. Y Sensitivity: Internal 371.030 nm {91} was used as internal standard for Zr 339.198 nm and Al 394.401 nm and Y 224.306 nm {450} for Al 167.079 nm. The content for B was monitored using B 249 nm line. The reported values were back calculated to the original catalyst sample using the original mass of the catalyst aliquot and the dilution volume. Catalyst Activity The catalyst activity is calculated on the basis of the following formula: amount of polymer produced (kg) Catalyst Activity (kg-PP / g-Cat / h) = catalyst loading (g) × polymerization time (h) The catalyst productivity is calculated on the basis of the following formula: amount of polymer produced (kg) Catalyst productivity (kg-PP / g-Cat) = catalyst loading (g) Polymer powder bulk density Instruments: Electronic balance: Range from 0,1g-11000g Graduated glass cylinder: Volume = max.250ml Plastic spoon: Volume=125ml Plastic funnel: D=105mm Execution: A glass cylinder is filled up to a volume of 250 ml by pouring in the unstabilised polymer powder, using a plastic spoon and a plastic funnel. Calculation: Mass of polymer (g) / measured volume (ml) XS The xylene soluble fraction (XS) as defined and described in the present invention was determined in line with ISO 16152 as follows: 2.5±0.1 g of the polymer were dissolved in 250 ml o-xylene under reflux conditions and continuous stirring, under nitrogen atmosphere. After 30 minutes, the solution was allowed to cool, first for 15 minutes at ambient temperature and then maintained for 30 minutes under controlled conditions at 25 ± 0.5 °C. The solution was filtered through filter paper. For determination of the xylene soluble content, an aliquot (100 ml) of the filtrate was taken. This aliquot was evaporated in nitrogen flow and the residue dried under vacuum at 100 °C until constant weight is reached. The xylene soluble fraction (weight percent) can then be determined as follows: Sensitivity: Internal XS% = (100 x m1x v0) / (m0x v1), wherein m0designates the initial polymer amount (grams), m1defines the weight of residue (grams), v0defines the initial volume (milliliter) and v1defines the volume of the analyzed sample (milliliter). To obtain the amorphous copolymer fraction for further characterization with GPC and NMR, the remaining xylene soluble filtrate was precipitated with acetone. The precipitated polymer was filtered and dried in the vacuum oven at 100 °C to constant weight. GPC: Molecular weight averages, molecular weight distribution, and polydispersity index (Mn, Mw, Mw / Mn) The MWD and the corresponded molecular weight averages Mn, Mw, Mvand Mzof the polymer sample were determined by using Gel Permeation Chromatography (GPC) at 160°C. All samples were integrated at the low Mw end up to the 3rdlast calibration point of the calibration curve (PS = 1820 g / mol ~ 1340 g / mol PP equivalent). A high temperature GPC equipped with a suitable concentration detector (like IR5 or IR4 from PolymerChar (Valencia, Spain), an online four capillary bridge viscometer (PL-BV 400-HT), and a dual light scattering detector (PL-LS 15 / 90 light scattering detector) with a 15° and 90° angle was used. 3x Olexis and 1x Olexis Guard columns from Agilent as stationary phase and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-Di tert butyl-4-methyl-phenol) as mobile phase at 160 °C and at a constant flow rate of 1 mL / min was applied. 200 μL of sample solution were injected per analysis. All samples were prepared by dissolving 8.0 – 10.0 mg of polymer in 10 mL (at 160 °C) of stabilized TCB (same as mobile phase) for 2,5 hours at 160°C under continuous gentle shaking. The injected concentration of the polymer solution at 160 °C (c160°C) was determined in the following way. 0,8772 With: w25 (polymer weight) and V25 (Volume of TCB at 25°C). The column set was calibrated using universal calibration (according to ISO 16014-2:2019) with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11500 kg / mol. The PS standards were dissolved at 160°C for 15 min or alternatively at room temperatures at a concentration of 0.2 mg / ml for molecular weight higher and equal 899 kg / mol and at a concentration of 1 mg / ml for molecular weight below 899 kg / mol. The conversion of the polystyrene peak molecular weight to polypropylene molecular weights is accomplished by using the Mark Houwink equation and the following Mark Houwink constants: Sensitivity: Internal KPS= 19 x 10-5ml / g, αPS= 0.655 KPP= 39 x 10-5ml / g, αPP= 0.725 A third order polynomial fit was used to fit the calibration data. All samples were prepared in the concentration range of 0.5 -1 mg / ml and dissolved at 160 °C for 3 hours under continuous gentle shaking Molecular weight averages (Mn, Mw, Mvand Mz), Molecular weight distribution (MWD) and its broadness, described by the polydispersity index PD= Mw / Mn(wherein Mnis the number average molecular weight and Mwis the weight average molecular weight) were determined using the following formulas: DSC The DSC curves and data have been produced on a DSC Q200 TA Instrument, by placing a 5-7 mg sample cut from the polymer MFR string, into a closed DSC aluminum pan, heating the sample from -10 °C to 225 °C at 10 °C / min, holding for 10 min at 225 °C, cooling from 225 °C to –30 °C, holding for 5 min at –30 °C, heating from –30 °C to 225 °C at 10 °C / min. The reported Tmvalues are those of the peak of the endothermic heat flow determined from the second heating scan. Melt Flow Rate The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g / 10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the molecular weight of the polymer. The Sensitivity: Internal MFR was determined at 230 °C and may be determined at different loadings such as 2.16 kg (MFR2) or 21.6 kg (MFR21). Comonomer content by FTIR Quantitative infrared (IR) spectroscopy was used to estimate the C2 content of the copolymers through calibration to a primary method (NMR spectroscopy). Calibration was facilitated through the use of a set of in-house, non-commercial calibration standards of known C2 contents determined by quantitative13C solution-state nuclear magnetic resonance (NMR) spectroscopy. The calibration procedure was undertaken in the conventional manner well documented in the literature [Spectroscopy of Polymers, 2nd Edition, J.L. Koenig, Elsevier Science, 1999]. The calibration set consisted of 8 calibration standards with C2 contents ranging between 0.0-3.5 wt%. Quantitative FTIR spectra were recorded in the solid-state using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded on 25x25 mm square films of 300 µm thickness prepared by compression moulding at 180 - 210°C and 70 bar of pressure. Standard transmission FTIR spectroscopy was employed using a spectral range of 5000-400 cm-1, an aperture of 6 mm, a spectral resolution of 2 cm-1, 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 32 and Norton Beer strong apodisation. Quantitative analysis was carried out by integration of (peak height) CH2rocking deformations at 732.5 cm-1(AQ) corresponding to isolated ethylene incorporation in PEP comonomer sequences (integration method K-OPUS, limits 759 and 702 cm-1). The quantitative band was normalized to the height of the CH combination band at 4323 cm-1(AR) corresponding to CH structural units (integration method K, limits 4480, 3950 cm-1). The C2 content in units of weight percent was then predicted from the normalized absorption (A0 = AQ / AR) using a linear calibration curve. The calibration curve having previously been constructed by least square regression of the normalized absorptions and comonomer contents measured by the primary technique (NMR Spectroscopy). The typical linear calibration curve has the form: ^ = ^^× ^^+ ^^Equation 1 Here C1is the slope of the calibration curve with 0.96 > C1> 1, and the intercept of -0.02 > C0> 0.06. The quality of the calibration was assessed using the usual Confidence of Determination (COD) or R2. The COD was around 0.998. Sensitivity: Internal NMR Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and content of regio-defects of the polypropylene homopolymers. Quantitative13C{1H} NMR spectra recorded in the solution-state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for1H and13C respectively. All spectra were recorded using a13C optimised 10 mm selective excitation probehead at 125°C using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 1,2- tetrachloroethane-d2(TCE-d2). This setup was chosen primarily for the high resolution needed for tacticity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci.26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed utilising the NOE and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson.187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 6144 (6k) transients were acquired per spectra using a 3 s recycle delay. Quantitative13C{1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts are internally referenced to the methyl signal of the isotactic pentad mmmm at 21.85 ppm. The tacticity distribution was quantified through integration of the methyl region between 23.6 and 19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci.26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules 30 (1997) 6251). The pentad isotacticity was determined through direct integration of the methyl region and reported as either the mole fraction or percentage of isotactic pentad mmmm with respect to all steric pentads i.e. [mmmm] = mmmm / sum of all steric pentads. When appropriate integrals were corrected for the presence of sites not directly associated with steric pentads. Characteristic signals corresponding to regio irregular propene insertion were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The presence of secondary inserted propene in the form of 2,1 erythro regio defects was indicated by the presence of the two methyl signals at 17.7 and 17.2 ppm and confirmed by the presence of other characteristic signals. The amount of 2,1 erythro regio defects was quantified using the average integral (e) of the e6 and e8 sites observed at 17.7 and 17.2 ppm respectively, i.e. e = 0.5 * (e6 + e8). Characteristic signals corresponding to other types of regio irregularity were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, Sensitivity: Internal F., Chem. Rev. 2000, 100, 1253). The amount of primary inserted propene (p) was quantified based on the integral of all signals in the methyl region (CH3) from 23.6 to 19.7 ppm paying attention to correct for other species included in the integral not related to primary insertion and for primary insertion signals excluded from this region such that p = CH3 + 2*e. The relative content of a specific type of regio defect was reported as the mole fraction or percentage of said regio defect with respect all observed forms of propene insertion i.e. sum of all primary (1,2), secondary (2,1) and tertiary (3,1) inserted propene units, e.g. [21e] = e / ( p + e + t + i ). The total amount of secondary inserted propene in the form of 2,1-erythro or 2,1-threo regio defects was quantified as sum of all said regio irregular units, i.e.

[0021] = [21e] + [21t]. Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the ethylene content and the isotacticity of the copolymers. Quantitative13C{1H} NMR spectra were recorded in the solution-state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for1H and13C respectively. All spectra were recorded using a13C optimised 10 mm extended temperature probehead at 125°C using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with chromium-(III)-acetylacetonate (Cr(acac)3) resulting in a 65 mM solution of relaxation agent in solvent as described in G. Singh, A. Kothari, V. Gupta, Polymer Testing 2009, 28(5), 475. To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single- pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson.187 (2007) 225 and V. Busico, P. Carbonniere, R. Cipullo, C. Pellecchia, J. Severn, G. Talarico, Macromol. Rapid Commun.2007, 28, 1128. A total of 6144 (6k) transients were acquired per spectra. Quantitative13C{1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Sensitivity: Internal With characteristic signals corresponding to 2,1 erythro regiodefects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 33, 1157) the correction for the influence of the regiodefects on determined properties was required. Characteristic signals corresponding to other types of regiodefects were not observed. Characteristic signals corresponding to the incorporation of ethylene were observed (as described in Cheng, H. N., Macromolecules 1984, 17, 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer: fE = ( E / ( P + E ) The comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33, 1157, through integration of multiple signals across the whole spectral region in the13C{1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents. The mole percent comonomer incorporation was calculated from the mole fraction: E [mol%] = 100 * fE The weight percent comonomer incorporation was calculated from the mole fraction: E [wt%] = 100 * ( fE * 28.06 ) / ( (fE * 28.06) + ((1-fE) * 42.08) ) The isotacticity of the copolymer was determined according to known methods, for example as described in Macromolecules 2005, vol.38, pp.3054-3059. The crystalline (CF) and soluble fractions (SF) of the heterophasic propylene resins as well as the comonomer content and intrinsic viscosities of the respective fractions were analysed by the Crystex method. The crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160°C, crystallization at 40°C and re- dissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160°C. Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an infrared detector (IR4) and an online 2-capillary viscometer is used for determination of the intrinsic viscosity (iV). IR4 detector is multiple wavelength detector detecting IR absorbance at two different bands (CH3 and CH2) for the determination of the concentration and the ethylene content Sensitivity: Internal in ethylene-propylene copolymers. IR4 detector is calibrated with series of EP copolymers with known ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13C- NMR). Amount of Soluble fraction (SF) and Crystalline Fraction (CF) are correlated through the XS calibration to the “Xylene Soluble” (XS) quantity and respectively Xylene Insoluble (XI) fractions, determined according to standard gravimetric method as per ISO16152 (2005). XS calibration is achieved by testing various EP copolymers with XS content in the range 2-31 wt%. Intrinsic viscosity (iV) of the parent EP copolymer and its soluble and crystalline fractions are determined with a use of an online 2-capillary viscometer and are correlated to corresponding iV determined in decalin according to ISO 1628-3 (2010). Calibration is achieved with several commercial EP PP copolymers with iV = 2-4 dL / g. A sample of the PP composition to be analysed is weighed out in concentrations of 10mg / ml to 20mg / ml. After automated filling of the vial with 1,2,4-TCB containing 250 mg / l 2,6-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample is dissolved at 160°C until complete dissolution is achieved, usually for 60 min, with constant stirring of 800rpm. A defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times. During the first injection the whole sample is measured at elevated temperature, determining the iV[dl / g] and the C2[wt%] of the PP composition. During the second injection the soluble fraction (at low temperature) and the crystalline fraction (at elevated temperature) with the crystallization cycle are determined (wt% SF, wt% C2, iV). Metallocene synthesis Synthesis of MC-CE1 Synthesis of this metallocene has been carried out as described in WO2019179959, MC- 2. Synthesis of MC-CE2 Synthesis of this metallocene has been carried out as described in WO2005058916, metallocene example 1. Sensitivity: Internal Synthesis of MC-IE2 Synthesis of 2-n-propyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene Method 1 2-Bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxyindan-1-ol Water (20 ml) was added to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy- 1H-indene (61.29 g, 0.2 mol) in a mixture of 550 ml of DMSO and 300 ml of THF. Then, 37.38 g (210 mmol, 1.05 equiv.) of N-bromosuccinimide was added in aliquots over 90 min. After that, the obtained mixture was stirred overnight at room temperature. Then, 1200 ml of water and 600 ml of dichloromethane were added. The organic layer was separated, and the aqueous layer was additionally extracted with 2 ^150 ml of dichloromethane. The combined organic extract was washed with 6 ^1000 ml of water, dried over Na2SO4, and evaporated to dryness. The residue was dissolved in 300 ml of hexane and left for crystallization for 30 min at 5 °C. The obtained white crystals were filtered off (G3), washed with n-hexane and dried in vacuum. This procedure gave 64.89 g of the title product. The combined filtrate was evaporated to dryness, and the residue was recrystallized in the same way from 35 ml of n-hexane. This procedure gave additional 8.07 g of the title product. Thus, the total yield of 2-bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5- methoxyindan-1-ol isolated in this synthesis was 72.96 g (90.4%).1H NMR (CDCl3): δ 7.34 (s, 1H), 6.99-6.94 (2s, sum 3H), 5.29 (dd, J = 6.2 Hz, J = 6.0 Hz, 1H), 4.17 (ddd, J = 7.7 Hz, J = 7.4 Hz, J = 6.0 Hz, 1H), 3.30 (dd, J = 16.4 Hz, J = 7.4 Hz, 1H), 3.24 (s, 3H), 3.06 (dd, J = 16.4 Hz, J = 7.7 Hz, 1H), 2.40 (d, J = 6.2 Hz, 1H), 2.35 (s, 6H), 1.42 (s, 9H).13C NMR (CDCl3): δ 158.21, 142.68, 137.99, 137.83, 136.83, 135.68, 131.99, 128.82, 127.14, 121.07, 83.74, 60.37, 54.83, 39.88, 35.30, 30.73, 21.38. Sensitivity: Internal 2-Bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene TsOH (2.0 g) was added to a solution of 2-bromo-6-tert-butyl-4-(3,5-dimethylphenyl)-5- methoxyindan-1-ol (72.96 g, 180.88 mmol) in 600 ml of toluene, preheated to ca.60 °C. This mixture was refluxed with Dean-Stark head for 7 min. Then, the reaction mixture was quickly cooled to room temperature using an ice-water bath. The formed solution was washed with 10% Na2CO3, the organic layer was separated, and the aqueous layer was extracted with 200 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then evaporated to dryness. The crude product was purified by flash chromatography on silica gel 60 (40-63 µm, hexanes-dichloromethane = 2:1) to give 70.51 g (ca. 100%) of 2-bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene as a light-yellow glassy solid.1H NMR (CDCl3): δ 7.24 (s, 1H), 7.05 (s, 2H), 6.99 (s, 1H), 6.87 (t, J = 1.6 Hz, 1H), 3.41 (d, J = 1.6 Hz, 2H), 3.26 (s, 3H), 2.36 (s, 6H), 1.43 (s, 9H).13C NMR (CDCl3): δ 155.18, 141.55, 141.19, 138.79, 137.91, 137.46, 132.79, 131.78, 128.82, 126.95, 123.25, 117.55, 60.65, 45.50, 35.19, 30.88, 21.40. 5 / 6-tert-Butyl-7 / 4-(3,5-dimethylphenyl)-6 / 5-methoxy-2-propyl-1H-indene [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](triphenylphosphine)dichloronickel(II) (NiCl2(IPr)PPh3 , 0.45 g, 0.57 mmol, 2.5 mol.%) was added to a mixture of 2-bromo-5-tert- butyl-7-(3,5-dimethylphenyl)-6-methoxy-1H-indene (8.1 g, 21 mmol) andnPrMgBr in THF (1.0 M, 105 ml, 5 equiv.). This solution was refluxed for 30 min. The dark solution formed was poured into a mixture of 200 g of ice and 200 ml of water. Then, 50 ml of 1.0 M HCl was added. The organic layer was separated. The aqueous layer was extracted with 4x100 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then evaporated to dryness. The product was isolated by flash-chromatography on silica gel 60 Sensitivity: Internal (40-63 µm, eluent: hexanes-dichloromethane = 10:1, vol). Yield 7.0 g of a slightly yellowish oil. This product was a mixture of two isomeric indenes contaminated with ca.9% of the debromination by-product. To reduce content of the debromination by-product, a mixture of this crude product (7.0 g) with 0.25 g TsOH in 100 ml of toluene was refluxed for 30 min. After the solution was cooled to room temperature 200 ml of an aqueous K2CO3was added, the organic layer was separated, and the aqueous layer was extracted with 2x40 ml of toluene. The combined organic extract was dried over K2CO3and then evaporated to dryness. The obtained material was distilled under reduced pressure to give 5.5 g (75%, purity ca.97%) of a ca.2:3 mixture of two isomers as a colorless oil, b.p.160–210°C / 3 mm Hg. Minor isomer:1H NMR (CDCl3): δ 7.34 (s, 1H), 7.10 (s, 2H), 6.98 (br. s, 1H), 6.34 (s, 1H), 3.30 (s, 2H), 3.25 (s, 3H), 2.38-2.34 (m, 8H), 1.59-1.50 (m, 2H), 1.44 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H).13C NMR (CDCl3): δ 156.08, 151.14, 144.16, 137.87, 137.72, 137.53, 137.43, 131.86128.28, 127.84, 125.40, 120.81, 60.44, 41.13, 35.04, 33.52, 31.11, 22.44, 21.42, 14.01. Major isomer:1H NMR (CDCl3): δ 7.23 (s, 1H), 7.09 (s, 2H), 6.98 (br. s, 1H), 6.45 (m, 1H), 3.25 (s, 3H), 3.12 (s, 2H), 2.38-2.34 (m, 8H), 1.59-1.50 (m, 2H), 1.44 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H).13C NMR (CDCl3): δ 154.24, 149.97, 141.56, 140.85, 140.44, 138.30, 137.65, 131.87, 128.46, 127.20, 126.05, 117.13, 60.65, 41.04, 35.12, 33.29, 31.00, 22.29, 21.42, 13.94. [6-tert-Butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-inden-1-yl] chlorodimethylsilane nBuLi in hexanes (2.5 M, 6.3 ml, 16.0 mmol) was added in one portion to a solution of 5- tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-propyl-1H-indene (5.5 g, 15.78 mmol) in a mixture of 120 ml of ether and 10 ml of THF cooled to –50 °C. This mixture was stirred overnight at room temperature, then the resulting yellow solution was cooled to –50 °C, and dichlorodimethylsilane (9.5 ml, 10.07 g, 78.0 mmol, 5.0 equiv.) was added in one portion. The resulting mixture was stirred overnight at room temperature, then filtered through a glass frit (G3), and the filter cake was washed with 2x50 ml of toluene. The Sensitivity: Internal combined filtrate was evaporated to dryness to give the title product which was used without further purification.1H NMR (CDCl3): δ 7.39 (s, 1H), 7.09 (br. s, 2H), 6.99 (s, 1H), 6.45 (s, 1H), 3.64 (s, 1H), 3.25 (s, 3H), 2.54-2.49 (m, 2H), 2.38 (s, 6H), 1.68-1.48 (m, 2H), 1.43 (s, 9H), 0.91 (t, J = 7.3 Hz, 3H), 0.42 (s, 3H), 0.15 (s, 3H).13C NMR (CDCl3): δ 155.79, 150.92, 143.54, 137.95, 137.56, 137.49, 136.54, 128.31, 127.89, 127.65, 125.43, 120.99, 60.46, 48.22, 35.16, 33.72, 31.16, 22.75, 21.44, 14.06, 1.19, -0.64. Method 2 n-Propylmalonic acid A solution of 99.7 g (1.78 mol) of potassium hydroxide in 500 cm3of water was added to a solution of 101.1 g (0.5 mol) of diethyl n-propylmalonate in 100 ml of methanol. The resulting mixture was refluxed for 5 h, then ethanol and methanol were distilled off. Then, 500 cm3of water was added, and the obtained mixture was acidified by 12 M HCl to pH 1.0. Propylmalonic acid was extracted with 4x400 ml of ether. The combined extract was evaporated to dryness, and the residue was dried in vacuum. This procedure gave 76.4 g (ca.100%) of n-propylmalonic acid which was used without further purification. 2-n-Propylacrylic acid Diethylamine (42.4 g, 0.58 mol) was added dropwise at 5 °C to a solution of ca.0.5 mol of n-propylmalonic acid in 650 ml of ethyl acetate. To the obtained suspension, 21.3 g (0.71 mol) of paraform was added. The resulting mixture was refluxed for 5 h, then cooled to 5oC, and 350 ml of ether and 1000 cm3of 2 M HCl were added. After mixing, the organic layer was separated, the aqueous layer was additionally extracted with 2x500 ml of ether. The combined organic extract was dried over Na2SO4 and then evaporated to dryness. The residue was purified by vacuum distillation to give 2-n-propylacrylic acid, bp 67-70oC / 4 mm Hg. Yield 46.1 g (80%) of a colorless liquid. Sensitivity: Internal1H NMR (CDCl3): δ 12.54 (br.s, 1H), 6.30 (m, 1H), 5.65 (m, 1H), 2.29 (t, J = 7.3 Hz, 2H), 1.52 (sext, J = 7.4 Hz, 2H), 0.94 (t, J = 7.4 Hz, 3H).13C NMR (CDCl3): δ 173.24, 140.02, 127.04, 33.44, 21.48, 13.58. 6-tert-Butyl-5-methoxy-2-n-propylindan-1-one 2-n-propylacrylic acid (46.1 g, 0.4 mol) was added to the Eaton's reagent obtained from 55 g of P4O10 and 280 ml of MeSO3H at 50 °C. To this mixture 52.5 g (0.32 mol) of 1-tert- butyl-2-methoxybenzene was added dropwise by vigorous stirring for ca.1 h at 50-53 °C. The resulting mixture was stirred for 1 h at this temperature, then cooled to room temperature and poured on a mixture of 0.5 liter of cold water and 1 kg of ice. The crude product was extracted with 3x300 ml of dichloromethane. The combined organic extract was washed by aqueous K2CO3, dried over K2CO3, filtered through a short pad of silica gel 60 (40-63 µm), and then evaporated to dryness. The residue was purified by vacuum distillation to give 62.6 g (75 %) of 6-tert-butyl-5-methoxy-2-n-propylindan-1-one as a yellowish oil (bp 155-170oC / 4 mm Hg).1H NMR (CDCl3): δ 7.67 (s, 1H), 6.87 (s, 1H), 3.93 (s, 3H), 3.23 (dd, J = 17.1 Hz, J = 7.6 Hz, 1H), 2.71 (dd, J = 17.1 Hz, J = 3.5 Hz, 1H), 2.66-2.60 (m, 1H), 1.94-1.88 (m, 1H), 1.51- 1.39 (m, 3H), 1.37 (s, 9H), 0.95 (t, J = 7.4 Hz, 3H).13C NMR (CDCl3): δ 207.76, 164.51, 154.70, 138.64, 129.18, 121.89, 107.70, 55.15, 47.41, 34.99, 33.83, 32.47, 29.53, 20.63, 14.05. 4-Bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1-one Bromine (6.2 ml, 19.2 g, 120 mmol) was added dropwise by vigorous stirring over 15 min to a mixture of 31.3 g (0.120 mol) of 6-tert-butyl-2-n-propyl-5-methoxyindan-1-one, 39.45 g of sodium acetate, 1.0 g ofnBu4NI, 100 ml of dichloromethane, and 200 ml of water at 5 °C. This mixture was stirred for 1 h at 5 °C, then a solution of 20 g of sodium acetate in 100 ml of water was added followed by addition of 3.1 ml (60 mmol) of bromine. The resulting mixture was additionally stirred for 1 h at this temperature and then washed by aqueous Na2SO3to remove an excess of bromine. The crude product was extracted with Sensitivity: Internal 3x100 ml of dichloromethane. The combined organic extract was dried over K2CO3, filtered through a pad of silica gel 60 (40-63 µm) and evaporated to dryness. Crystallization of the residue from ca.50 ml of n-pentane at -15oC gave 33.2 g of the title product (81.6%).1H NMR (CDCl3): δ 7.69 (s, 1H), 4.03 (s, 3H), 3.22 (dd, J = 18.3 Hz, J = 8.4 Hz, 1H), 2.72- 2.65 (m, 2H), 1.97-1.88 (m, 1H), 1.54-1.43 (m, 3H), 1.40 (s, 9H), 0.97 (t, J = 7.3 Hz, 3H).13C NMR (CDCl3): δ 207.70, 162.75, 154.24, 145.43, 133.15, 121.38, 116.66, 61.64, 47.52, 35.66, 34.04, 33.64, 30.62, 20.59, 14.03. 6-tert-Butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one A mixture of 16.6 g (48.9 mmol) of 4-bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1-one, 9.45 g (63.0 mmol, 1.28 equiv.) of 3,5-Me2C6H3B(OH)2, 0.26 g (0.5 mmol, 1 mol.%) of Pd(PtBu3)2, 15.8 g of Na2CO3, 80 ml of 2-methyltetrahydrofurane, and 75 ml of water was refluxed for 6 h. Further on, 100 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 2x50 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then evaporated to dryness. The product was purified by flash-chromatography on silica gel 60 (40-63 um, eluent: dichloromethane- hexane = 2:1, vol.). The combined elute was evaporated to dryness, the residue was washed by 30 ml of n-pentane and dried in vacuum. This procedure gave 15.7 g (88.0%) of title product.1H NMR (CDCl3): δ 7.73 (s, 1H), 7.03 (s, 1H), 7.02 (s, 2H), 3.31 (s, 3H), 3.06 (dd, J = 17.3 Hz, J = 7.6 Hz, 1H), 2.58 (m, 1H), 2.49 (dd, J = 17.3 Hz, J = 3.8 Hz, 1H), 2.39 (s, 6H), 1.94-1.84 (m, 1H), 1.42 (s, 9H), 1.40-1.34 (m, 3H), 0.91 (t, J = 7.3 Hz, 3H).13C NMR (CDCl3): δ 208.45, 163.41, 153.09, 143.21, 138.06, 136.28, 132.67, 131.33, 129.07, 127.17, 121.14, 60.48, 47.51, 35.33, 33.67, 32.20, 30.50, 21.37, 20.62, 14.02. 5-tert-Butyl-2-n-propyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene Sensitivity: Internal NaBH4(2.44 g, 64.6 mmol) was added to a solution of 6-tert-butyl-2-n-propyl-5-methoxy- 4-(3,5-dimethylphenyl)-indan-1-one (15.7 g, 43 mmol) in 180 ml of THF cooled to 5 °C. To this mixture, 70 ml of MeOH was added dropwise over ca.5 h at 5 °C, and the resulting mixture was stirred overnight at room temperature. Then, this mixture was evaporated to dryness, 200 ml of dichloromethane and 200 ml water were added to the residue, and the so obtained mixture was acidified with 2 M HCl to pH~6.5. The organic layer was separated, the aqueous layer was additionally extracted with 2x50 ml of dichloromethane. The combined organic extract was evaporated to dryness. TsOH (300 mg) was added to a solution of the residue in 300 ml of toluene. This mixture was refluxed with Dean-Stark head for 10 min and then cooled to room temperature using a water bath. The formed solution was washed with 10% Na2CO3, the organic layer was separated, the aqueous layer was extracted with 2x50 ml of dichloromethane. The combined organic extract was dried over K2CO3and then evaporated to dryness. The product was purified by flash- chromatography on silica gel 60 (40-63 µm, eluent: dichloromethane-hexane = 1:1, vol.) and dried in vacuum to give 14.0 g (93.4%) of pure product as a mixture of two isomeric indenes.1H NMR (CDCl3): δ 7.34 (s), 7.23 (s), 7.10 (s), 7.09 (s), 6.98 (s), 6.45 (m), 6.34 (s), 3.30 (s), 3.25 (s), 3.12 (s), 2.38-2.34 (m), 1.55 (sextet, J = 7.4 Hz), 1.44 (s), 0.91 (t, J = 7.3 Hz).13C NMR (CDCl3): δ 156.08, 154.24, 151.14, 149.97, 144.16, 141.56, 140.85, 140.44, 138.30, 137.87, 137.72, 137.65, 137.53, 137.43, 131.87, 128.46, 128.28, 127.84, 127.20, 126.05, 125.40, 120.81, 117.13, 60.65, 60.44, 41.13, 41.04, 35.12, 35.04, 33.52, 33.29, 31.11, 31.00, 22.44, 22.29, 21.42, 14.01, 13.94. [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4- (3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-inden-1-yl]dimethylsilane Sensitivity: InternalnBuLi in hexanes (2.5 M, 3.17 ml, 7.92 mmol) was added in one portion to a suspension of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (3.0 g, 7.92 mmol) in a mixture of 40 ml of ether and 35 ml of THF cooled to -50 °C.4,8-di(3,5-dimethylphenyl)- 6-methyl-1,2,3,5-tetrahydro-s-indacene was produced as described in WO 2019 / 189959 (Synthesis of MC-2). The resulting mixture was stirred overnight at room temperature, then the so obtained light-orange solution with a large amount of orange precipitate was cooled to -50 °C, and 75 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at - 25 °C, then a solution of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-propyl-5-methoxy-1H- inden-1-yl]chlorodimethylsilane (3.5 g, 7.93 mmol) in 50 ml of THF was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 µm), which was additionally washed by 2x50 ml of ether. The combined organic elute was evaporated to dryness. The crude product was purified by flash chromatography on silica gel 60 (40-63 µm, 600 ml, eluent: hexanes: dichloromethane = 5:1, vol.). This procedure gave 4.7 g (76%, purity ca.98%) of the title product (as a ca.2:3 mixture of two stereoisomers) as a colorless glassy solid. Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen- 1-yl][2-propyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl] zirconium dichloride (MC-IE2) nBuLi in hexanes (2.5 M, 4.8 ml, 12.0 mmol) was added in one portion to a solution of 4.7 g (6.0 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1- yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-propyl-1H-inden-1-yl]dimethylsilane in 50 ml of di-n-butyl ether t room temperature. This mixture was stirred overnight at room temperature, then the resulting red solution was cooled to 0oC in an ice-bath, and 1.4 g (6.0 mmol) of ZrCl4was added. The reaction mixture was stirred for 24 h at room Sensitivity: Internal temperature to give an orange-red suspension. This mixture was evaporated to dryness. This solid was extracted with 50 ml of hot toluene. On the evidence of NMR spectroscopy, the obtained extract included a ca.4:1 mixture of anti- and syn-zirconocene dichlorides. This extract was evaporated to dryness, and 30 ml of hexane was added. The yellow precipitate fallen from the obtained solution at room temperature was collected and dried in vacuum. This procedure gave 3.1 g of anti-zirconocene dichloride contaminated with di- n-butyl ether which was further recrystallized from a mixture of ca.5 ml of toluene and 15 ml of hexane to give 1.45 g of yellow powder of anti-zirconocene dichloride containing 0.5 mol of toluene per mol of the complex, so the adjusted net weight of the isolated anti- complex was 1.38 g (24%). Anal. calc. for C56H64Cl2OSiZr*0.5(C7H8): C, 72.23; H, 6.93. Found: C, 72.15; H, 7.21.1H NMR (CDCl3): δ 7.42 (s, 1H), 7.25 (very br. s, 4H), 7.14 (s, 1H), 7.03 (s, 1H), 6.99 (s, 1H), 6.96 (s, 1H), 6.94 (s, 1H), 6.81 (s, 1H), 6.59 (s, 1H), 3.39 (s, 3H), 3.13-3.03 (m, 2H), 2.97-2.90 (m, 1H), 2.57-2.43 (m, 2H), 2.41 (s, 3H), 2.37 (s, 3H), 2.34 (12H), 2.29 (s, 3H), 2.18-2.11 (m, 1H), 2.05-1.97 (m, 1H), 1.81-1.70 (m, 1H), 1.35 (s, 9H), 1.30-1.18 (m, 2H), 1.14 (s, 3H), 0.82 (t, J = 7.3 Hz, 3H), -0.13 (s, 3H).13C NMR (CDCl3): δ 159.90, 144.63, 144.17, 143.25, 141.39, 139.87, 138.39, 138.06, 137.74 (br. s), 137.22, 136.84, 134.70, 134.44, 132.03, 131.99, 131.72, 130.56, 129.02, 128.81, 128.69, 127.90, 127.52, 126.91, 123.55, 123.38, 121.17, 120.33, 81.89, 81.61, 62.65, 35.68, 34.06, 33.94, 32.39, 30.40, 26.97, 26.04, 21.56, 21.47, 21.41, 21.25, 19.86, 13.87, 3.83, 2.31. Synthesis of MC-IE1 Synthesis of the second indene pre-ligand: 2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6 tert-butylindene Method A 6-tert-Butyl-5-methoxy-2-ethylindan-1-one 4.76 g (47.5 mmol, 1.27 equiv.) of 2-ethylacrylic acid was added to the Eaton's reagent obtained from 8.28 g of P4O10 and 52 ml of MeSO3H at 50 °C. To this rapidly stirred mixture 6.17 g (37.5 mmol) of 1-tert-butyl-2-methoxybenzene was added dropwise for ca.1 h at 48-50 °C (water bath temperature). The resulting mixture was stirred for 1 h at this Sensitivity: Internal temperature, then cooled to room temperature, and poured on a mixture of 0.4 liter of cold water and 0.1 kg of ice. The crude product was extracted with 3x50 ml of dichloromethane, and 100 ml of hexane was added. The combined organic extract was filtered through a pad of silica gel 60 (40-63 µm, 20 ml), which was additionally washed by 2x25 ml of a 1:1 mixture of hexane and dichloromethane. The elute was evaporated to dryness. The crude product was dissolved in 100 ml of dichloromethane; the formed solution was washed by aqueous K2CO3, dried over K2CO3and then evaporated to dryness to give 8.5 g (92 %, ca.90% purity) of 6-tert-butyl-5-methoxy-2-ethylindan-1-one as a yellowish oil. 4-Bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one 6.95 ml (21.57 g, 135 mmol) of bromine was added dropwise over 5 min to a mixture of 33.2 g (135 mmol) of 6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 41.7 g of sodium acetate, 1.0 g ofnBu4NBr, 135 ml of dichloromethane, and 230 ml of water at 5 °C. This mixture was stirred for 1 h at 5 °C, then a solution of 19.0 g of sodium acetate in 120 ml of water was added followed by addition of 3.5 ml (10.79 g, 67.5 mmol) of bromine. The resulting mixture was additionally stirred for 1 h at this temperature and then washed by aqueous Na2SO3to remove excess bromine. The crude product was extracted by 4x70 ml of dichloromethane. The combined organic extract was dried over K2CO3, filtered through a pad of silica gel 60 (40-63 µm, 20 ml), the filtrate was evaporated to dryness, and the residue was dried in vacuum. This procedure gave 42.85 g (97.5%, ca.90% purity) of 4- bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one as a yellowish oil which was used without further purification. 6-tert-Butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one A mixture of 41.2 g (126.5 mmol) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 21.8 g (145.5 mmol, 1.15 equiv.) of 3,5-Me2C6H3B(OH)2, 0.65 g (1.3 mol. %) of Pd(PtBu3)2, 40.7 g of Na2CO3, 210 ml of 2-methyltetrahydrofurane, and 185 ml of water was refluxed Sensitivity: Internal for 6 h. Further on, 100 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 2x50 ml of dichloromethane. The combined organic extract was evaporated to dryness, the residue was dissolved in 100 ml of hexane, the obtained solution was filtered through a pad of silica gel 60 (40-63 µm, 20 ml), the elute was evaporated to dryness, and the residue was crystalized from 50 ml of pentane. This procedure gave 21.6 g of pure 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)- indan-1-one. The mother liquor was evaporated followed by recrystallization of the formed oil in the same manner from 10 ml of pentane at room temperature. This procedure gave 4.2 g of a white powder. Crystallization of the residue from 20 ml of pentane at -15 °C gave 6.3 g of 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one (90% purity). Overall yield 32.1 g (72.3%, purity ca.98%) of a slightly yellowish crystalline solid. 5-tert-Butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene 0.81 g (21.4 mmol, 0.75 equiv.) of NaBH4was added to a solution of 10.0 g (28.5 mmol) of 6-tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 14.0 ml of THF cooled to 17 °C. To this mixture, 10.7 ml of MeOH was added dropwise for ca.2 h, and the resulting mixture was stirred overnight at room temperature. Then, this mixture was evaporated to dryness, 50 ml of dichloromethane and 100 ml water were added to the residue, and thus obtained mixture was acidified with 2 M HCl to pH~6.5. The organic layer was separated, the aqueous layer was additionally extracted with 3x30 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a grey oil. To a solution of this oil in 75 ml of toluene 0.045 g of TsOH was added. This mixture was refluxed with Dean-Stark head for 9 min and then cooled to room temperature using water bath. The formed solution was washed with 10% Na2CO3, the organic layer was separated, the aqueous layer was extracted with 3x50 ml of dichloromethane. The combined organic extract was dried over K2CO3and then evaporated to dryness. The residue was dissolved in 100 ml of hexane, the obtained solution was filtered through a pad of silica gel 60 (40-63 µm, 10 ml) (which was additionally washed by 2x50 ml of hexane), the elute was evaporated to dryness, and the residue was dried in vacuum to give 9.3 g (98.6%) of 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene as a yellowish oil. Sensitivity: Internal [6-tert-Butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]chlorodimethyl silane 5.53 ml (13.8 mmol) of 2.5 MnBuLi in hexanes was added in one portion to a solution of 4.59 g (13.7 mmol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-ethyl-6-methoxy-1H-indene in 100 ml of ether cooled to -50 °C. This mixture was stirred overnight at room temperature, then the resulting orange-yellow solution was cooled to -50 °C, and 8.25 ml (5.0 equiv.) of dichlorodimethylsilane was added in one portion. The resulting mixture was stirred overnight at room temperature, then filtered through a glass frit (G3), and the filter cake was washed with 2x20 ml of toluene. The combined filtrate was evaporated to dryness to give 5.7 g (97.5%) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1- yl](chloro)-dimethylsilane as a yellowish thick oil which was used without further purification. [4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4- (3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-inden-1-yl]dimethylsilane 2.47 ml (6.17 mmol) of 2.5 MnBuLi in hexanes was added in one portion to a suspension of 2.33 g (6.15 mmol) of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s- indacene in a mixture of 27 ml of ether and 8 ml of THF cooled to -50 °C. The resulting Sensitivity: Internal mixture was stirred overnight at room temperature, then the so obtained light-orange solution with a large amount of orange precipitate was cooled to -50 °C, and 45 mg of CuCN was added. The reaction mixture temperature was allowed to rise to -17 °C for ca. 0.5 h, and then a solution of 2.65 g (6.2 mmol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2- ethyl-5-methoxy-1H-inden-1-yl](chloro)dimethylsilane in 45 ml of ether was added in one portion to this suspension. This mixture was stirred overnight at room temperature, then evaporated to dryness. The residue was dissolved in a mixture of 90 ml of hexane and 10 ml of dichloromethane, the obtained solution was filtered through a pad of silica gel 60 (40- 63 µm, 15 ml) (which was additionally washed by 2x25 ml of a 10:1 mixture of hexane and dichloromethane), the elute was evaporated to dryness, and the residue was dried in vacuum to give 5.0 g of the title product (a ca.60:40 mixture of the stereoisomers) as a white powder which was used without further purification. Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen- 1-yl][2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride (MC-IE1) 5.0 ml (12.5 mmol) of 2.5 MnBuLi in hexanes was added in one portion to a yellowish solution of 5.0 g (ca. 6.2 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7- tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H- inden-1-yl]dimethylsilane in 32 ml ofnBu2O at 0 °C. This mixture was stirred overnight at room temperature, then the resulting red turbid solution was cooled to 0 °C in an ice-bath, and 1.45 g (6.2 mmol) of ZrCl4 was added. The reaction mixture was stirred for 24 h at room temperature to give an orange-red suspension. This suspension was evaporated to dryness (to the state of an orange powder). To this solid 40 ml of pentane was added. The Sensitivity: Internal yellow precipitate fallen from this mixture at room temperature was collected and dried in vacuum. This procedure gave 4.2 g of a 99:1 mixture of anti- and syn-zirconocene dichlorides contaminated with ca.0.52 g of LiCl. Therefore, the title complex was obtained in ca.63% yield. Method B 6-tert-Butyl-5-methoxy-2-ethylindan-1-one 4.76 g (47.5 mmol, 1.27 equiv.) of 2-ethylacrylic acid was added to the Eaton's reagent obtained from 8.28 g of P4O10and 52 ml of MeSO3H at 50 °C. To this rapidly stirred mixture, 6.17 g (37.5 mmol) of 1-tert-butyl-2-methoxybenzene was added dropwise over ca.1 h at 48-50 °C. The resulting mixture was stirred for 1 h at this temperature, then cooled to room temperature, and poured on a mixture of 0.4 liter of cold water and 0.1 kg of ice. The crude product was extracted with 3x50 ml of dichloromethane, and 100 ml of hexane was added. The combined organic extract was filtered through a pad of silica gel 60 (40-63 µm, 20 ml), which was additionally washed by 2x25 ml of a 1:1 mixture of hexane and dichloromethane, the obtained elute was evaporated to dryness. The crude product was dissolved in 100 ml of dichloromethane, the formed solution was washed by aqueous K2CO3, dried over K2CO3, and then evaporated to dryness to give 8.5 g (92%, ca. 90% purity) of 6-tert-butyl-5-methoxy-2-ethylindan-1-one as a yellowish oil. 4-Bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one 1.7 ml (5.26 g, 35.8 mmol) of bromine was added dropwise over 5 min to a mixture of 8.1 g (32.9 mmol) of 6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 10.0 g of sodium acetate, 0.3 g ofnBu4NBr, 30 ml of dichloromethane, and 60 ml of water at 5 °C. This mixture was stirred for 1 h at 5 °C, then a solution of 4.63 g of sodium acetate in 26 ml of water was added followed by addition of 0.85 ml (2.63 g, 16.4 mmol) of bromine. The resulting mixture was additionally stirred for 1 h at this temperature and then washed by aqueous Na2SO3 to remove an excess of bromine. The crude product was extracted by 3x50 ml of Sensitivity: Internal dichloromethane. The combined organic extract was evaporated to dryness. The residue was dissolved in a mixture of 35 ml of hexane and 35 ml of dichloromethane, the obtained solution was filtered through a pad of silica gel 60 (40-63 µm, 20 ml) (which was additionally washed by 2x35 ml of a 1:1 mixture of hexane and dichloromethane), the elute was evaporated to dryness, and the residue was dried in vacuum. This procedure gave 9.67 g (90.4%, purity ca. 95%) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one as a yellowish oil which was used without further purification. 6-tert-Butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one A mixture of 9.67 g (29.7 mmol) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 4.9 g (32.7 mmol, 1.1 equiv.) of 3,5-Me2C6H3B(OH)2, 0.15 g (1 mol. %) of Pd(PtBu3)2, 9.57 g of Na2CO3, 50 ml of 2-methyltetrahydrofurane, and 44 ml of water was refluxed for 6 h. Then, 100 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 3x40 ml of dichloromethane. The combined organic extract was evaporated to dryness, the residue was dissolved in 100 ml of hexane, the obtained solution was filtered through a pad of silica gel 60 (40-63 µm, 20 ml) (which was additionally washed by 2x35 ml of hexane), and the elute was evaporated to dryness. Yield 9.72 g (93.4%, purity ca.94%) of a slightly yellowish oil. 5-tert-Butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene NaBH4 (0.78 g, 20 mmol, 0.75 equiv.) was added to a solution of 9.62 g (27.4 mmol) of 6- tert-butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one in 13.75 ml of THF cooled to 17 °C. To this mixture 10.3 ml of MeOH was added dropwise for ca.2 h, and the resulting mixture was stirred overnight at room temperature. Then, this mixture was evaporated to dryness, 50 ml of dichloromethane and 50 ml water were added to the residue, and thus obtained mixture was acidified with 2 M HCl to pH~6.5. The organic layer Sensitivity: Internal was separated, the aqueous layer was additionally extracted with 3x30 ml of dichloromethane. The combined organic extract was evaporated to dryness to give 9.62 g of a grey oil. To a solution of this oil in 72 ml of toluene 0.043 g of TsOH was added. This mixture was refluxed with Dean-Stark head for 9 min and then cooled to room temperature using water bath. The formed solution was washed with 10% Na2CO3, the organic layer was separated, the aqueous layer was extracted with 3x50 ml of dichloromethane. The combined organic extract was evaporated to dryness, the residue was dissolved in 100 ml of hexane, the obtained solution was dried over K2CO3, filtered through a pad of silica gel 60 (40-63 um, 10 ml) (which was additionally washed by 2x50 ml of hexane), the elute was evaporated to dryness, and the residue was dried in vacuum to give 8.5 g (92.7%, purity ca. 97%) of 5-tert-butyl-2-ethyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene as a yellowish oil. Synthesis of the ligand and metallocene MC-IE1 using the 5-tert-butyl-2-ethyl-6-methoxy- 7-(3,5-dimethylphenyl)-1H-indene obtained with method B. [6-tert-Butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]chlorodimethyl silane nBuLi in hexanes (2.5 M, 0.444 ml, 1.11 mmol) was added in one portion to a solution of 5-tert-butyl-7-(3,5-dimethylphenyl)-2-ethyl-6-methoxy-1H-indene (0.37 g, 1.1 mmol) in 4 ml of nBu2O cooled to 0 °C. This mixture was stirred overnight at room temperature, then 0.33 ml (2.5 equiv.) of dichlorodimethylsilane was added in one portion. After 5 min 0.86 ml of Et2O was added, and the resulting mixture was stirred overnight at room temperature and used without further purification. Sensitivity: Internal [4,8-Bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5- dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]dimethylsilane The substituted indene reacted withnBuLi in ether at –20 °C, this mixture was stirred for 2 h. Then, THF was added, and the reaction mixture was allowed to stay overnight. After that, CuCN catalyst was added at –20°C, the reaction mixture was stirred for 30 min at - 20 °C followed by addition of the chloroindenylsilane at the same temperature. This procedure resembles very much the standard conditions except that CuCN was added at –20 °C rather than at –50 °C. Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen- 1-yl][2-ethyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride 5.2 ml (13 mmol) of 2.5 MnBuLi in hexanes was added in one portion to a yellowish solution of 5.05 g (ca. 6.5 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s- indacen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-ethyl-1H-inden-1- Sensitivity: Internal yl]dimethylsilane in 32 ml ofnBu2O at 0 °C. This mixture was stirred overnight at room temperature, then the resulting red turbid solution was cooled to 0 °C in an ice-bath, and 1.51 g (6.5 mmol) of ZrCl4was added. The reaction mixture was stirred for 24 h at room temperature to give an orange-red suspension. This mixture was evaporated to dryness (to the state of orange powder). To this solid 40 ml of pentane was added. The yellow solid precipitated from this mixture at room temperature was collected and dried in vacuum (4.0 g of a 99:1 mixture of anti- and syn-zirconocene dichlorides contaminated with ca.0.54 g of LiCl, therefore, yield was ca.57%). Synthesis of MC-IE3 Synthesis of the second indene pre-ligand: 4,8-Bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5- tetrahydro-s-indacene 2-Ethylacryloyl chloride One drop of DMF was added to a solution of 77.1 g (0.77 mol) of 2-ethylacrylic acid in 600 ml of dichloromethane cooled in an ice bath. Then, to the resulting solution, 108 g (0.85 mol) of oxalyl chloride was added dropwise over 1 h, and the reaction mixture was stirred overnight at room temperature. The formed mixture was concentrated, and the residue was distilled in vacuum to give 65 g (71.2%) of 2-ethylacryloyl chloride as a colorless liquid, b.p.55-75oC / 100 mbar.1H NMR (CDCl3): δ 6.55 (s, 1H), 6.02 (s, 1H), 2.39 (q, J = 7.4 Hz, 2H), 1.12 (t, J = 7.4 Hz, 3H).13C NMR (CDCl3): δ 168.73, 146.60, 132.03, 25.33, 12.55. 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one, method A 2-Ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one A mixture of 65.0 g (548 mmol) of 2-ethylacryloyl chloride and 65.0 g (548 mmol) of indane was added dropwise over 15 min to a suspension of 182 g (1.37 mol) of AlCl3in 1000 ml of dichloromethane cooled to 0 °C. The cooling bath was then removed, and this solution was stirred overnight at room temperature. The reaction mixture was poured onto 2 kg of crushed ice, the organic phase was separated, and the aqueous phase was extracted with Sensitivity: Internal 3x200 ml of dichloromethane. The combined organic extract was washed by aqueous K2CO3, dried over K2CO3, passed through a short pad of silica gel 60 (40-63 µm). The elute was evaporated to dryness. The formed oil was distilled under vacuum to give 80.92 g (ca.74%, purity ca.70%) of a slightly yellowish oil, b.p. 130-145oC / 3 mm Hg. The so obtained 2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one was used without further purification.1H NMR (CDCl3): δ 7.52 (s, 1H), 7.24 (s, 1H), 3.20 (dd, J1= 7.8 Hz, J2= 17.1 Hz, 1H), 2.94-2.86 (m, 4H), 2.71 (dd, J1= 3.6 Hz, J2= 17.0 Hz, 1H), 2.59-2.54 (m, 1H), 2.13-2.05 (m, 2H), 1.96-1.90 (m, 1H), 1.56-1.45 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H).13C NMR (CDCl3): δ 208.05, 152.68, 152.60, 143.74, 135.46, 121.77, 118.67, 48.89, 32.79, 31.74, 25.52, 24.31, 11.30. 4,8-Dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one A solution of 80.9 g (ca.404 mmol) of 2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one (as prepared above, ca.70% purity) in 200 ml of dichloromethane was added dropwise over 15 min to a suspension of 134.7 g (1.01 mol, 2.5 equiv.) of AlCl3in 400 ml of dichloromethane at –10 °C. The reaction mixture was stirred for 10 min at this temperature, then 41.7 ml (129.4 g, 809 mmol, 2.0 equiv.) of bromine was added dropwise over 1 h. The resulting mixture was stirred overnight at room temperature and then poured onto 1000 cm3of crushed ice. The organic layer was separated, the aqueous layer was extracted with 3x300 ml of dichloromethane. The combined organic extract was washed with aqueous K2CO3, dried over K2CO3, passed through a short pad of silica gel 60 (40-63 µm), and the obtained elute was evaporated to dryness. The crude product was roughly purified by crystallization from 500 ml of n-hexane to give 89.5 g of crude product. The following crystallization of this crude product from 500 ml of n-hexane gave analytically pure product. The mother liquor from the last crystallization was evaporated to ca.200 ml to give a white suspension of the product in hexane. This suspension was heated to the boiling point (~65-70 °C) and then filtered (while hot) through glass frit (G3). The so obtained precipitate was dried under vacuum to give one more crop of the title product. The overall yield was 59.9 g (41%).1H NMR (CDCl3): δ 3.17-3.05 (m, 5H), 2.70-2.60 (m, 2H), 2.17 (quin, J = 7.7 Hz, 2H), 2.03-1.93 (m, 1H), 1.59-1.48 (m, 1H), 1.02 (t, J = 7.4 Hz, Sensitivity: Internal 3H).13C NMR (CDCl3): δ 204.94, 154.85, 152.52, 146.90, 134.22, 117.80, 115.17, 49.83, 35.64, 34.60, 32.30, 24.53, 23.18, 11.47. 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one A mixture of 59.9 g (167 mmol) of 4,8-dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)- one, 56.4 g (376 mmol, 2.25 equiv.) of 3,5-dimethylphenylboronic acid, 1.34 g of Pd(PtBu3)2, 95.8 g of Na2CO3, 600 ml of 2-methyltetrahydrofurane, and 420 ml of water was refluxed for 7 h. Then, 600 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 300 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then evaporated to dryness to give a brown solid mass. The product was isolated by column chromatography on silica gel 60 (40-63 µm, d 50 mm, l 400 mm, eluent: hexanes-dichloromethane = 1:3, vol.). The elute was evaporated to dryness followed by trituration of the residue with 300 ml of n-hexane. The obtained suspension was filter through glass frit (G3), and thus obtained white precipitate was washed with 2x30 ml of n-hexane and then dried under vacuum. Yield 61.47 g (90%).1H NMR (CDCl3): δ 7.03 (s, 1H), 6.99 (s, 1H), 6.95 (s, 2H), 6.92 (s, 2H), 3.08 (dd, J1= 8.7 Hz, J2= 18.0 Hz, 1H), 2.88-2.68 (m, 4H), 2.57-2.49(m, 2H), 2.39 (s, 6H), 2.36 (s, 6H), 2.04- 1.84 (m, 3H), 1.47-1.36 (m, 1H), 0.91 (t, J = 7.4 Hz, 3H).13C NMR (CDCl3): δ 207.37, 151.81, 149.90, 143.55, 138.22, 137.93, 137.23, 136.88, 135.89, 135.43, 132.40, 128.93, 126.74, 126.49, 49.72, 33.03, 31.96, 31.06, 25.64, 24.30, 21.46, 21.41, 11.66. 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one, method B 2-Ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one 4.76 g (47.5 mmol, 1.27 equiv.) of 2-ethylacrylic acid was added to the Eaton's reagent obtained from 8.28 g of P4O10 and 52 ml of MeSO3H at 50oC. To this rapidly stirred mixture 4.43 g (37.5 mmol) of indane (~95% purity) was added dropwise for ca.45 min at 48-50oC. The resulting mixture was stirred for 1 h at this temperature, then cooled to room Sensitivity: Internal temperature, and poured on a mixture of 0.4 liter of cold water and 0.1 kg of ice. The crude product was extracted with 3 x 50 ml of dichloromethane, and 75 ml of hexane was added. The combined organic extract was filtered through a pad of silica gel 60 (40-63 um, 20 ml), which was additionally washed by 2 x 40 ml of a 1:2 mixture of hexane and dichloromethane. The elute was evaporated to dryness. The crude product was dissolved in 100 ml of dichloromethane; the formed solution was washed by aqueous K2CO3, dried over K2CO3, and then evaporated to dryness to give 7.15 g (95%, ca.60% purity) of 2- ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one as a yellow oil. 4,8-Dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one A solution of 7.0 g (ca. 35 mmol) of 2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one (as prepared above, ca.60% purity) in 10 ml of dichloromethane was added dropwise over 15 min to a suspension of 11.6 g (87 mmol) of AlCl3in 40 ml of dichloromethane at –10 °C. The reaction mixture was stirred for 10 min at this temperature, then 4.0 ml (12.4 g, 77.5 mmol, 2.2 equiv.) of bromine was added dropwise over 1 h at –10 °C. The resulting mixture was stirred overnight at room temperature and then poured onto 100 cm3of crushed ice. The organic layer was separated, the aqueous layer was extracted with 3x30 ml of dichloromethane. The combined organic extract was passed through a short pad of silica gel 60 (40-63 µm, 40 ml), the silica gel layer was additionally washed with 2x30 ml of dichloromethane, and the obtained elute was evaporated to dryness. The obtained oil was dissolved with 50 ml of hexane. After 5 min, a black precipitate formed was filtered off. Crystallization of the filtrate at –15 °C overnight gave 6.4 g of crude solid product. This crude product was dissolved in a mixture of 25 ml of n-hexane and 6 ml toluene at reflux. The following crystallization (from the boiling point to RT) gave 4 g of the desired product slightly contaminated with polymeric by-products. The mother liquor from the last crystallization was evaporated to dryness. Crystallization of the residue from a mixture of 10 ml of hexane and 1 ml of toluene gave one more crop (0.9 g) of the product. Thus obtained 4.9 g of the solid product was dissolved in 20 ml of a 1:1 mixture of hexane and dichloromethane, and this solution was passed through a short pad of silica gel 60 (40-63 µm, 15 ml). The silica gel layer was additionally washed with 2x20 ml of a 1:1 mixture of hexane and dichloromethane. The combined elute was evaporated to dryness to give 4.6 g (37%) of the title product as a yellowish solid. Sensitivity: Internal 4,8-Bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one A mixture of 4.3 g (12 mmol) of 4,8-dibromo-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)- one, 4.14 g (27.6 mmol, 2.3 equiv.) of 3,5-dimethylphenylboronic acid, 0.1 g of Pd(PtBu3)2, 6.9 g of Na2CO3, 43 ml of 2-methyltetrahydrofurane, and 30 ml of water was refluxed for 7 h. Then, 50 ml of dichloromethane was added, the organic layer was separated, and the aqueous layer was extracted with 2x30 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then evaporated to dryness. The solid mass was dissolved in 30 ml of a 2:3 mixture of hexane and dichloromethane, and the formed solution was passed through a short pad of silica gel 60 (40-63 µm, 20 ml). The silica gel layer was washed with 3x20 ml of a 1:1 mixture of hexane and dichloromethane, and the obtained elute was evaporated to dryness. The solid residue was treated with 20 ml of pentane, the formed suspension was filtered through glass frit (G3), the precipitate was dried in vacuum to give 3.8 g of the title product. The mother filtrate was evaporated to ca.10 ml. to form a suspension that was filtered through glass frit (G3). The residue was dried under vacuum to give one more crop (0.95 g) of the title product. The overall yield 4.75 g (97%, purity 98%). 4,8-Bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indacene Methanol (100 ml) was added dropwise over 5 h to a mixture of 20.0 g (49 mmol) of 4,8- bis(3,5-dimethylphenyl)-2-ethyl-3,5,6,7-tetrahydro-s-indacen-1(2H)-one and 4.28 g (109 mmol) of NaBH4 in 300 ml of THF at 0-5 °C. The obtained mixture was stirred overnight at room temperature and then evaporated to dryness.400 ml of dichloromethane and 1000 ml of water were added to the residue, and the so obtained mixture was acidified by 2 M Sensitivity: Internal HCl to pH~6.5. The organic layer was separated, the aqueous layer was additionally extracted with 2x200 ml of dichloromethane. The combined organic extract was dried over Na2SO4and evaporated to dryness to give a white solid mass. TsOH (1.0 g) was added to a solution of this solid mass in 350 ml of toluene, preheated to ca.60 °C. This mixture was refluxed with Dean-Stark head for 12 min. Then, the reaction mixture was quickly cooled to room temperature using an ice-water bath. The formed solution was washed with 10% Na2CO3, the organic layer was separated, the aqueous layer was extracted with 100 ml of dichloromethane. The combined organic extract was dried over K2CO3and then evaporated to dryness. The crude product was purified by flash chromatography on silica gel 60 (40-63 µm, d 50 mm, l 30 mm, hexanes-dichloromethane = 10:1, vol). This procedure gave 19.4 g (100%) of the title product as a white solid.1H NMR (CDCl3): δ 7.05 (s, 2H), 7.03 (s, 2H), 6.98 (s, 2H), 6.44 (m, 1H), 3.25 (s, 2H), 2.89 (t, J =7.3 Hz, 2H), 2.83 (t, J =7.3 Hz, 2H), 2.42-2.33 (m, 14H), 1.98 (quin, J =7.3 Hz, 2H), 1.10 (t, J =7.4 Hz, 3H).13C NMR (CDCl3): δ 151.79, 142.60, 140.88, 140.24, 140.19, 139.83, 138.42, 137.55, 137.39, 133.53, 129.79, 128.39, 128.18, 127.32, 126.60, 124.41, 40.59, 32.78, 32.51, 26.09, 24.45, 21.42, 13.44. [4,8-Bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4- (3,5-dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]dimethylsilane nBuLi in hexanes (2.5 M, 3.84 ml, 9.6 mmol) was added in one portion to a solution of 4,8- bis(3,5-dimethylphenyl)-6-ethyl-1,2,3,5-tetrahydro-s-indacene (3.77 g, 9.6 mmol) in a mixture of 40 ml of ether and 40 ml of THF at -50 °C. This mixture was stirred overnight at room temperature, then the resulting greenish-yellow suspension was cooled to -50 °C, and 100 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at -20 °C, then a solution of 4.1 g (9.6 mmol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5- methoxy-1H-inden-1-yl](chloro)dime-thylsilane in 50 ml of THF was added in one portion. Sensitivity: Internal The formed mixture was stirred for 12 h at room temperature, then filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by 2x50 ml of ether. The combined organic elute was evaporated to dryness. The crude product was purified by flash chromatography on silica gel 60 (40-63 µm, 600 ml, eluent: hexanes: dichloromethane = 5:1, vol.). This procedure gave 5.10 g (6.5 mmol, yield ca.67.8%, purity ca.98%) of the title product (as a ca 40:60 mixture of the stereoisomers) as a glassy solid. Anti-dimethylsilanediyl[η5-4,8-bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s- indacen-1-yl][η5-6-tert-butyl-4-(3,5-dimethylphenyl)-2-ethyl-5-methoxyinden-1-yl] zirconium dichloride (MC-IE3) nBuLi in hexanes (2.5 M, 5.1 ml, 12.75 mmol) was added in one portion to a solution of [4,8-bis(3,5-dimethylphenyl)-2-ethyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5- dimethylphenyl)-2-ethyl-5-methoxy-1H-inden-1-yl]dimethylsilane (5.00 g, 6.38 mmol) in 50 ml of di-n-butyl ether at room temperature. This mixture was stirred for 5 h at room temperature, then the resulting solution was cooled to 0 °C in an ice bath, and ZrCl4(1.49 g, 6.39 mmol) was added. The formed mixture was stirred for 24 h at room temperature to give a yellow suspension. This suspension was evaporated to dryness, and the residue was extracted with 50 ml of warm toluene. The precipitate was filtered off (G4). On the evidence of NMR spectroscopy, the resulting filtrate included a ca.95 / 5 mixture of anti- and syn-zirconocene dichlorides. This filtrate was evaporated to dryness, and 30 ml of hexane was added. The orange precipitate fallen from this solution overnight at room temperature was filtered off (G3), washed with 10 ml of n-hexane, and then dried in vacuum. This procedure gave 4.8 g of anti-zirconocene dichloride (contaminated with ca. 0.6% of syn-isomer) containing ca. 0.02 mol of ether per mol of Zr and 0.08 mol of n- hexane per mol of Zr, so the adjusted net weight of the isolated complex was ca.4.75 g (yield ca.79%). Sensitivity: Internal Anal. calc. for C56H64Cl2OSiZr.: C, 71.30; H, 6.84. Found: C, 71.45; H, 7.02.1H NMR (CDCl3): δ 7.65-6.7 (very br.s, 4H), 7.38 (s, 1H), 7.09 (s, 1H), 7.02 (s, 1H), 6.99 (s, 1H), 6.96 (s, 1H), 6.95 (s, 1H), 6.86 (s, 1H), 6.60 (s, 1H), 3.40 (s, 3H), 3.11-2.86 (m, 4H), 2.60- 2.25 (m, 22H), 1.99 (m, 1H), 1.82-1.70 (m, 1H), 1.35 (s, 9H), 1.14-1.10 (m, 6H), 0.90 (t, J = 7.4 Hz, 3H), -0.16 (s, 3H).13C NMR (CDCl3): δ 159.82, 144.81, 144.09, 143.11, 141.75, 141.49, 141.12, 138.40, 138.16, 137.77 (br.s), 137.38, 136.92, 134.52, 132.25, 132.12, 131.74, 130.93, 128.96, 128.85, 128.79, 128.70, 127.89, 127.50 (br.s), 126.85, 122.95, 121.18, 120.77, 119.34, 81.54, 80.54, 62.68, 35.63, 33.91, 32.38, 30.39, 26.52, 26.07, 25.86, 21.46, 21.41, 21.27, 17.00, 16.59, 4.20, 2.38. Catalyst synthesis, used chemicals MAO Axion CA133030 wt-% solution in toluene was purchased from Chemtura / Lanxess and used as received and stored at –20 °C for not longer than 6 months. All the chemicals and chemical reactions were handled under an inert gas atmosphere using Schlenk and glovebox techniques, with oven-dried glassware, syringes, needles or cannulas. All catalysts have been prepared using silica Sunspera AGC DM-L-303, calcined at 600 °C. All catalysts have been prepared using silica Sunspera AGC DM-L-303, calcined at 600 °C. Catalyst preparations The catalysts were prepared by following a two-step preparation method. First step was the preparation of SiO2 / MAO (activated carrier), followed by a second step where a toluene solution of the metallocene complex was impregnated on the dry support from the first step. Only in case the metallocene was not enough soluble in toluene, a second aliquot of MAO was added to the metallocene / toluene slurry in order to promote the full dissolution of the metallocene. Preparation of SiO2 / MAO activated carrier A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen. 10 kg of SiO2 carrier was first added from a feeding drum into the reactor, followed by careful pressurizing and depressurizing with nitrogen. Then, toluene (43.5 kg) was added. The SiO2 / toluene slurry was stirred for 25 min at 22 °C. Then, 18 kg of 30 wt% MAO in toluene (Axion CA 1330) was added slowly (140 min) through a 12 mm line on the top of the reactor keeping the temperature around 22 °C. After MAO addition, the reactor Sensitivity: Internal temperature was quickly increased to 90 °C and the mixture was stirred at this temperature for 120 min. Then the hot toluene was filtered out and the solid cake was washed twice with hot toluene while stirring (43.5 kg, 90 °C, 30 min, 40 rpm). Each time the hot toluene was filtered out. Finally the solid cake was dried with slow stirring (5 rpm) under vacuum for 9 h at 80 °C. Synthesis of SiO2 / MAO / MC-CE1 = Comparison catalyst 1 (CE1) In a nitrogen filled glovebox, dry toluene (2.5 mL) was added to an aliquot of metallocene MC-CE1 (32.3 mg). The mixture was stirred for 30 minutes at room temperature. Next, 2.0 g of the silica / MAO carrier was placed in a glass vial. The solution of metallocene in toluene was added dropwise by means of a syringe to the SiO2 / MAO carrier over the course of 5 minutes with gentle mixing. The resulting mixture was shaken well and allowed to stay for 1 hour. The resulting solid was dried under vacuum for 1 hour at 60 °C to yield the catalyst as a light red free flowing powder Synthesis of SiO2 / MAO / MC-CE2 = Comparison catalyst 2 (CE2) In a nitrogen filled glovebox, dry toluene (2.5 mL) was added to 26.4 mg of metallocene C in a septum bottle. The solution was stirred for 30 minutes at room temperature but it did not dissolve. Then MAO (0.1 mL) was added and the mixture was stirred for an additional 30 minutes to make it dissolve completely. Next, 2.0 g of SiO2 / MAO was placed in a septum bottle. The solution of metallocene in toluene was added dropwise by means of a syringe to the SiO2 / MAO carrier over the course of 5 minutes with gentle mixing. The resulting powder was allowed to rest for 1 hour, then it was transferred into a Schlenk flask and dried under vacuum for 1 hour at 60 °C to yield the catalyst as light red free-flowing powder (1.96 g). Synthesis of SiO2 / MAO / MC-IE1 = Inventive catalyst 1 (IE1-1) In a nitrogen filled glovebox, dry toluene (5 mL) was added to 60.2 mg of metallocene anti- MC-IE1 in a septum bottle. The solution was stirred for 30 minutes at room temperature. Next, 0.2 mL of a 30 wt% solution of methylalumoxane (MAO) in toluene (Axion CA1330) was added and the solution stirred for additional 30 min. Then, the solution of metallocene and MAO in toluene was added dropwise by means of a syringe to 4.003 g of SiO2 / MAO in a septum bottle carrier over the course of 10 minutes with gentle mixing. The resulting powder was allowed to rest for 1 hour, then it was transferred into a Schlenk flask and dried under vacuum for 1 hour and 45 min at 60 °C to yield the catalyst as a light red free- flowing powder. Sensitivity: Internal Synthesis of SiO2 / MAO / MC-IE1 = Inventive catalyst 2 (IE1-2) In a nitrogen filled glovebox, dry toluene (2.5 mL) was added to 16.20 mg of metallocene anti-MC-IE1 in a septum bottle. The solution was stirred for 30 minutes at room temperature but it stayed hazy. Then MAO (0.1 mL) was added and the mixture was stirred for an additional 30 minutes to make it dissolve completely. Next, 2.009 g of SiO2 / MAO was placed in a septum bottle. The solution of metallocene in toluene was added dropwise by means of a syringe to the SiO2 / MAO carrier over the course of 5 minutes with gentle mixing. The resulting powder was allowed to rest for 1 hour, then it was transferred into a Schlenk flask and dried under vacuum for 1 hour at 60 °C to yield the catalyst as a pink and free flowing powder. Synthesis of SiO2 / MAO / MC-IE1 = Inventive catalyst 3 (IE1-3) In a nitrogen filled glovebox, dry toluene (2.5 mL) was added to 40.7 mg of metallocene anti-MC-IE1 in a septum bottle. The solution was stirred for 30 minutes at room temperature but it stayed hazy. Then MAO (0.1 mL) was added and the mixture was stirred for an additional 30 minutes to make it dissolve completely. Next, 2.002 g of SiO2 / MAO was placed in a septum bottle. The solution of metallocene in toluene was added dropwise by means of a syringe to the SiO2 / MAO carrier over the course of 5 minutes with gentle mixing. The resulting powder was allowed to rest for 1 hour, then it was transferred into a Schlenk flask and dried under vacuum for 1 hour at 60 °C to yield the catalyst as a pink and free flowing powder. Synthesis of SiO2 / MAO / MC-IE1 = Inventive catalyst 4 (IE1-4) In a nitrogen filled glovebox, dry toluene (2.5 mL) was added to 20.3 mg of metallocene anti-MC-IE1 in a septum bottle. The solution was stirred for 30 minutes at room temperature but it stayed hazy. Then MAO (0.1 mL) was added and the mixture was stirred for an additional 30 minutes to make it dissolve completely. Next, 2.000 g of SiO2 / MAO was placed in a septum bottle. The solution of metallocene in toluene was added dropwise by means of a syringe to the SiO2 / MAO carrier over the course of 5 minutes with gentle mixing. The resulting powder was allowed to rest for 1 hour, then it was transferred into a Schlenk flask and dried under vacuum for 1 hour at 60 °C to yield the catalyst as a pink and free flowing powder. Synthesis of SiO2 / MAO / MC-IE2 = Inventive catalyst 5. (IE5) In a nitrogen filled glovebox, dry toluene (2.5 mL) was added to 28.4 mg of metallocene anti-MC-IE2 in a septum bottle. The solution was stirred for 30 minutes at room temperature. Next, 2.000 g of SiO2 / MAO was placed in a septum bottle. The solution of Sensitivity: Internal metallocene in toluene was added dropwise by means of a syringe to the SiO2 / MAO carrier over the course of 5 minutes with gentle mixing. The resulting powder was allowed to rest for 1 hour, then it was transferred into a Schlenk flask and dried under vacuum for 1 hour at 60 °C to yield the catalyst as a red free-flowing powder. Synthesis of SiO2 / MAO / MC-IE3 = Inventive catalyst 6. (IE6) In a nitrogen filled glovebox, dry toluene (2.5 mL) was added to 28.4 mg of metallocene anti-MC-IE3 in a septum bottle. The solution was stirred for 30 minutes at room temperature. Next, 2.000 g of SiO2 / MAO was placed in a septum bottle. The solution of metallocene in toluene was added dropwise by means of a syringe to the SiO2 / MAO carrier over the course of 5 minutes with gentle mixing. The resulting powder was allowed to rest for 1 hour, then it was transferred into a Schlenk flask and dried under vacuum for 1 hour at 60 °C to yield the catalyst as a light red free-flowing powder. The metallocene content in each catalyst is calculated from mass balance. The values are listed in Table 3: Table 3: catalysts tested and their metallocene content Metallocene Catalyst Al MC in catalyst * # wt% wt% MC-CE1 CE1 14.8 1.59 MC-CE2 CE2 13.2 1.28 MC-IE1 IE1-1 12.0 1.46 IE1-2 13.7 0.79 IE1-3 13.4 1.96 IE1-4 12.8 0.99 MC-IE2 IE5 12.3 1.40 MC-IE3 IE6 12.6 1.36 * MC=metallocene; metallocene content in the dry catalyst calculated from mass balance Polymerization examples Monomers and gases Hydrogen (quality 6.0) was supplied by Air Liquide and used as received. Propylene, quality 2.3, and ethylene have been purified by passing through columns filled with Sensitivity: Internal PolyMax301 T-4427B (60°C; Cu / CuO), Molecular sieve MS13X-APG 1 / 16 and Selexsorb COS 1 / 8. Propylene and propylene / ethylene 2-step polymerization procedure (20-L reactor, liquid + gas phase) Step 1: Propylene homo polymerization in bulk, 20-L reactor A stainless-steel reactor equipped with a ribbon stirrer, with a total volume of 20.9 dm³ (R1) or 21.2 dm³ (R2) containing 0.2 bar-g propylene, was filled with additional 4.45 kg propylene. Triethylaluminium (0.8 ml of 0.62 molar solution in n-heptane) was added using a stream of 250 g propylene, then the chosen amount of H2 (see Tables) was added via mass flow controller in one minute. The reactor temperature was stabilized at 25 °C (HB- Therm) and the solution was stirred and 250 rpm for at least 20 min. Then the catalyst was injected as described in the following. The desired amount of solid catalyst was loaded into a 5 ml stainless steel vial; alternatively the chosen amount of a catalyst slurry in oil, after shaking for about 5 min in a glass vial, was drawn with a syringe and loaded into the 5 ml stainless steel vial. Then the catalyst vial was mounted on a port on the lid of the reactor. The catalyst was fed into the reactor by flushing 350 g propylene from the balance through the catalyst vial. Stirring speed was kept at 250 rpm and pre-polymerization was run for 10 minutes at either 25 or 30 °C. Then the polymerization temperature was increased to the set value. The second aliquot of H2 was added at 60 °C over 2 min. The reactor temperature was kept constant throughout the polymerization. The polymerization time was measured starting when the temperature was 2 °C below the set polymerization temperature. When the set polymerization time has lapsed, the reaction was stopped by injecting 5 ml ethanol, cooling the reactor and simultaneously flashing the volatile components. After purging the reactor 3 times with N2 and one vacuum / N2 cycle, the reactor was opened, the polymer powder was taken out and dried overnight in a fume hood. 100 g of the polymer was additivated with 0.5 wt% Irganox B225 (dissolved in acetone) and then dried overnight in a fume hood and additionally one hour in a vacuum drying oven at 60 °C. Step 2: Ethylene-propylene copolymerization in gas phase, 20-L reactor Step 2 was performed as follows. After the bulk homopolymerization step was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced to 0.4 bar-g by venting the monomers. The stirrer speed was set to 180 rpm and the reactor temperature Sensitivity: Internal was set to 70 °C. Then the reactor pressure was increased to 20 bar-g by feeding a defined C3 / C2 gas mixture (see tables). The C3 / C2 ratio was defined by where C2 / C3 was the weight ratio of the two monomers and R was their relative reactivity ratio, determined experimentally. In the present experiments, the value of R was set at 0.40. The temperature was held constant by thermostat and the pressure was kept constant by feeding via mass flow controller a C3 / C2 gas mixture of composition corresponding to the target polymer composition and by thermostat, until the set time for this step had expired. Then the reactor was cooled down (to about 30 °C) and the volatile components flashed out. After purging the reactor 3 times with N2 and one vacuum / N2 cycle, the product was taken out and dried overnight in a fume hood.100 g of the polymer was additivated with 0.5 wt% Irganox B225 (solution in acetone) and dried overnight in a hood followed by 2 hours in a vacuum drying oven at 60°C. Heterophasic polymerization results The performance of the catalysts prepared from different metallocenes in liquid propylene polymerization were compared. The conditions are described in Table 4A and the results are shown in Table 4B. Table 4A: Propylene polymerisation conditions Prepoly step Transition tnuo . g n o pinio tlet m . ditslyo p s l atp e me n p m etea elkmyaats eimH2 H2 Ttrf2rtru b alyTatH epx E Cata Sfoimmo C Trfmg °C min NL NL °C min 1CE172 30 10 0,50 2,52 60 16 2 CE2 89 25 10 0,50 2,52 60 19 3 IE1 50 30 10 0,50 2,52 60 16 4IE255 30 10 0,50 2,52 60 16 5 IE3 48 30 10 0,50 2,52 60 16 6 IE4 58 30 10 0,50 2,52 60 16 7IE561 30 10 0,50 2,52 60 16 8IE663 30 10 0,50 2,52 60 16 Sensitivity: Internal (Table 4A continued.) Bulk stepGas phase stepn sa s s le2iop H .it gp e s o n ntesin n nera a .g gdio idiou p e n e n e mlaxatm o eim artlku a eithfs eitnfs s n s mis eimd ais h d ah E T T T ebp 2 a 3 aerT T efp efp imm CrtCrtP 2 3 TorfC C NL°C min min g g barg °C min g g 1 3,02 75 40 15 246,8 299,3 20 70120 60,1 180,5 2 3,02 75 40 11 250,3 304,8 20 70120157,6 473,0 3 3,02 75 40 12 253,8 310,3 20 70120 86,5 276,6 4 3,02 75 40 11 245,3 300,5 20 70120 82,2 263,0 5 3,02 75 40 11 246,6 302,1 20 70120 75,1 250,1 6 3,02 75 40 11 245,5 300,1 20 70120 80,6 256,8 7 3,02 75 40 11 246,4 301,0 20 70120 59,0 177,2 8 3,02 75 40 11 244,2 298,0 20 70120 61,8 186,1 Table 4B: Results on whole material y e lepl itld avit ln yitaec vitmiere cre olc a v u v u x Y datd E OorOe porm p g kg / gcat kg / gMC 1 817 11,3 714 2 1140 12,8 1001 3 1410 28,2 1932 4 1242 22,6 2866 5 1031 21,5 1096 6 1173 20,2 2051 7 1065 17,5 1247 8 1104 17,5 1289 Sensitivity: Internal Table 4B (cont’d) ne n cie y sry r oita edit2 e leplv hlka itpwu s Rd b n F w Tc Tm mta e c s o e o a P d M p Max e g E kgPP / gMC / h g / ml g / 10min °C °C 1 189 0,45 13,0 112 151 2 533 0,38 62,8 116 157 3 465 0,40 16,5 114 154 4 741 0,41 19,1 116 154 5 320 0,40 18,2 116 154 6 548 0,42 17,9 115 155 7 248 0,44 30,1 115 153 8 261 0,43 28,2 116 156 Table 4C: Results on soluble fraction Analysis soluble fraction leCrystex GPC p max SF iV (SF) Mw Mw / Mn E wt% dl / g g / mol 1 25,5 4,5 561000 2,8 2 54,3 3,4 338000 3,7 3 26,5 4,8 704000 2,7 4 27,7 5,1 631000 2,7 5 29,8 4,9 572500 3,2 6 27,1 4,9 630000 2,8 7 21,5 4,6 537500 2,5 8 21,6 4,5 556000 2,5 le(Table 4C continued.) p m Solution 13C NMR ax E C2 C2 RC2 / C32,1e E-2,1 rExrPwt% mol% mol% mol% 1 23,76 31,86 0,38 0,00 0,16 1,3 2 23,41 31,43 0,37 0,00 0,18 1,5 3 23,31 31,32 0,37 0,00 0,20 1,3 4 22,85 30,76 0,36 0,00 0,14 1,3 5 23,31 31,31 0,37 0,00 0,32 1,3 6 23,04 30,99 0,37 0,00 0,10 1,3 7 23,65 31,72 0,38 0,00 0,17 1,3 8 25,12 33,47 0,41 0,00 0,00 1,2 Sensitivity: Internal We have discovered that borate-free catalysts based on the metallocenes of the invention can produce heterophasic copolymers with improved rubber iV / matrix Tm / productivity overall balance than catalysts based on the prior art catalysts (CE1, CE2 metallocenes). In particular, we can produce heterophasic copolymers with higher matrix melting point (therefore higher stiffness) while keeping the highest iV capability, and therefore improving the stiffness / impact balance of the materials. Sensitivity: Internal

Claims

CLAIMS 1. A metallocene complex of formula (I)wherein Mt is Zr or Hf; X is a sigma ligand; R1are each independently, same or different from each other, C1-C20 hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8 ring; R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or a C6-C9-aryl, provided that R2and R2’ are not both methyl; R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20aryl, or -OR31, with R31being C1-C10-hydrocarbyl, whereby at least one R3per phenyl group and at least one R4is not H; R5and R6are each independently, same or different from each other, C1-C10hydrocarbyl, or may form together with the C atoms they are attached to a C5-C7carbocycle; R51’ is C1-C10-hydrocarbyl; and R6’ is C(R61)3, with R61being linear or branched C1-C6-alkyl.

2. A metallocene complex of formula (I) as claimed in claim 1 having formula (I-a) Sensitivity: Internalwherein Mt is Zr or Hf; X is a sigma ligand; n is 1 to 3, such as 1, 2 or 3, preferably 3; R1are each independently, same or different from each other, C1-C20 hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8-ring; R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or a C6-C9-aryl, provided that R2and R2’ are not both methyl; R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-20-arylalkyl, C7-20-alkylaryl, C6-20 aryl, or -OR31, with R31being C1-C10-hydrocarbyl, whereby at least one R3per phenyl group and at least one R4is not H; R51’ is C1-C10-hydrocarbyl; and R6’ is C(R61)3, with R61being linear or branched C1-C6-alkyl.

3. A metallocene complex of formula (I) as claimed in claim 1 or 2 having formula (I-b) Sensitivity: Internalwherein Mt is Zr or Hf; X is a sigma ligand; R1are each independently, same or different from each other, C1-C20 hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8-ring; R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H or linear or branched C1-C6-alkyl, provided that R2and R2’ are not both methyl; R3and R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-20-arylalkyl, C7-20-alkylaryl, C6-20aryl, or -OR31, with R31being C1-C10-hydrocarbyl,whereby at least one R3per phenyl group and at least one R4is not H.

4. A metallocene complex as claimed in any one of claims 1 to 3, wherein one or two R3per phenyl group are not H and on both phenyl groups the R3are the same, and two R4on the phenyl group are not H and these two R4are the same.

5. A metallocene complex as claimed in claim 4, wherein two R3per phenyl group are not H and on both phenyl groups the R3are linear or branched C1-C6-alkyl, preferably methyl, and two R4on the phenyl group are not H and these two R4are linear or branched C1-C6 alkyl, preferably methyl. Sensitivity: Internal6. A metallocene complex as claimed in any one of the preceding claims, wherein R2and R2’ are each independently, same or different from each other, CH2-R21, with R21being H or linear or branched C1-C6-alkyl; preferably H or linear C1-C6alkyl; preferably H or linear C1-C4alkyl, more preferably H, methyl or ethyl, provided that R2and R2’ are not both methyl.

7. A metallocene complex as claimed in any one of the preceding claims, wherein one of R2and R2’ is methyl, and the other is of the formula CH2-R21, with R21being linear or branched C1-C6-alkyl; preferably linear or branched C1-C4-alkyl; more preferably methyl or ethyl.

8. A metallocene complex as claimed in any one of claims 1 to 6, wherein neither R2nor R2’ are methyl.

9. A metallocene complex as claimed in claim 8, wherein R2and R2’is each independently, same or different from each other, CH2-R21, with R21being linear or branched C1-C6-alkyl, more preferably linear or branched C1-C4-alkyl, even more preferably methyl or ethyl, yet more preferably methyl.

10. A metallocene complex as claimed in any one of the preceding claims, wherein R1are each independently, same or different from each other, C1-C10 hydrocarbyl, preferably C1-C6 alkyl, preferably methyl.

11. A metallocene complex as claimed in claim 10, wherein R1are the same and a C1-C10hydrocarbyl, preferably C1-C6 alkyl, preferably methyl.

12. A polymerization catalyst, comprising, preferably consisting of (i) a metallocene complex of formula (I); (ii) a cocatalyst system comprising a cocatalyst comprising a group 13 element; and (iii) optionally a support.

13. The polymerization catalyst according to claim 12, wherein cocatalyst (ii) is an alumoxane cocatalyst, preferably in the absence of any further cocatalysts.

14. The polymerization catalyst as claimed in claim 12 or 13, supported on silica.

15. A process for the polymerization of propylene, comprising polymerizing propylene and optionally at least one of comonomer selected from ethylene or C4-C10-alpha olefin Sensitivity: Internalcomonomers in the presence of a polymerization catalyst claimed in any one of claim 12 to 14.

16. A process for the preparation of a heterophasic polypropylene copolymer comprising (I) polymerizing propylene in bulk in the presence of a polymerization catalyst as claimed in claim 12 to 14 to form a polypropylene homopolymer matrix; (II) in the presence of said polypropylene homopolymer matrix and said polymerization catalyst and in the gas phase, polymerizing propylene and ethylene to form a heterophasic polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber.

17. A process for the preparation of a heterophasic polypropylene copolymer comprising (I) polymerizing propylene in bulk in the presence of polymerization catalyst as claimed in claim 12 to 14 to form a polypropylene homopolymer; (II) in the presence of said polypropylene homopolymer and said polymerization catalyst and in the gas phase, polymerizing propylene to form a polypropylene homopolymer matrix; (III) in the presence said polypropylene homopolymer matrix and said polymerization catalyst and in the gas phase, polymerizing propylene and ethylene to form a heterophasic polypropylene copolymer comprising a polypropylene homopolymer matrix and ethylene propylene rubber (EPR).

18. An indene of formula (II)wherein the dotted lines represent a double bond present in between carbons 1 and 2 or 2 and 3 of the indenyl ring; Sensitivity: InternalR2’ is CH2-R21, with R21being linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6- C9-aryl; R4are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20-aryl, or -OR31, with R31being C1- C10-hydrocarbyl, whereby at least one R4is not H; R51’ is C1-C10-hydrocarbyl; and R6’ is C(R61)3, with R61being linear or branched C1-C6-alkyl. Sensitivity: Internal

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