PROCESS FOR PREPARING ETHYLENE POLYMERS HAVING LONG CHAIN BRANCHES

FIELD OF THE INVENTION

The present invention relates to a process for preparing ethylene polymers having long chain branches via a polymerization of ethylene in the presence of a catalyst system comprising a bridged metallocene catalyst and an alkenyl-aluminum compound as activating agent. Said bridged metallocene catalyst is optionally provided on an inert support. The process has the advantage of allowing the control of long chain branching in ethylene polymers thereby allowing the preparation of ethylene polymers with tailored properties. The present invention also relates to long chain branched ethylene polymers obtained by the present process.

BACKGROUND OF THE INVENTION

Polyolefins, such as polyethylene compositions, are used for the production of a wide variety of articles. The use of a particular polyolefins in a particular application will depend on the type of physical and/or mechanical properties displayed by the polymer. Thus, there is an ongoing need to develop polymers that display novel physical and/or mechanical properties and methods for producing these polymers.

Processing behaviour of polymers has been shown to be strongly dependent on their properties such as molecular weight (Mw), polydispersity (Mw/Mn), stereoregularity and, more generally, their molecular architecture (linear, branched or cross-linked). In particular, long chain branching is a key resin parameter as it has huge effects on rheology but remains very difficult to control.

In general polymers containing long chain branches (LCBs) exhibit a better processability than their linear counterparts. Such a characteristic can be expressed in terms of melt strength, which is defined as the maximum tension applicable to a polymer melt without breaking. LCB polymers possess high melt strength while poor melt strength is observed with materials composed by mainly linear chains. High melt strength polymers are highly desirable for industry-relevant processes, for example in the blow moulding of plastic bottles.

In-reactor technologies to prepare LCB-polymers are mainly linked to the used catalyst structure in combination with the process. However, with existing approaches, it remains difficult to obtain a polyolefin with a certain desired amount of long chain branching.

The amount of long chain branching can be modified with post-reactor technologies such as high-energy electron beam irradiation, peroxide curing and grafting, however leading to increased costs. Also, due to the radical mechanisms involved in these treatments, ample control over LCB formation is rather impossible; hence, in this case, polymers with complex structures are obtained. Moreover, such post-reactor treatments may cause polymer degradation and affect the positive properties of PE and are intrinsically expensive.

There is therefore a demand for processes for preparing polyethylene having tailored properties, and especially controlling the amount of long chain branching preferably over a wide range. There is in particular a demand in the art for an improved process to prepare ethylene polymers having long chain branches, and preferably having controlled amounts of long chain branches.

It is therefore an object of the present invention to provide a process for preparing ethylene polymers having long chain branches which is more controllable. It is also an object of the present invention to provide a process for preparing ethylene polymers having long chain branches which is widely applicable and less expensive.

It is in particular an object of the present invention to provide a process for preparing ethylene polymers with LCBs during polymer synthesis. In other words, it is an object to provide an “in-reactor” process for preparing ethylene polymers having long chain branches. Another object of the present invention to provide a process that allows in reactor production of ethylene polymers (polyethylene) having tailored amounts, e.g. controlled amounts of long chain branches.

SUMMARY OF THE INVENTION

It has now surprisingly been found that the above objectives can be attained either individually or in any combination by using the specific and well-defined process as disclosed herein for preparing ethylene polymers with long chain branches.

In a first aspect, the present invention provides a process for preparing ethylene polymers having long chain branches, said process comprising the steps of feeding into at least one reactor ethylene monomer and optionally one or more alpha-olefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and optionally one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm; and wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent.

In an embodiment, the invention provides a process wherein the alkenyl-aluminum compound of formula (I) is applied during said polymerization process at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

In a preferred embodiment of the invention, a process is provided, wherein said at least one bridged metallocene catalyst is immobilized on an inert support.

In a preferred embodiment of the invention, a process is provided, wherein the alkenyl- aluminum compound of formula (I) is not provided on a support.

In a preferred embodiment of the invention, a process is provided, wherein the alkenyl- aluminum compound of formula (I) is not provided on the inert support of the catalyst.

In certain embodiments of the invention, a process is provided, wherein said polymerisation process is a homopolymerisation process of said ethylene monomer in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and preferably at a concentration comprised between 10 and 3000 ppm, or between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

In certain embodiments of the invention, a process is provided, wherein said polymerisation process is a copolymerisation process of said ethylene monomer and said one or more alpha-olefins comonomer(s) in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, and said alkenyl-aluminum compound of formula (I) is applied during said copolymerisation process at a concentration of at most 1000 ppm, and preferably at a concentration comprised between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

A process according to the invention allows to fine-tune the amount of long chain branching in ethylene polymer during the polymerization process. The present process also allows a reduction of costs as compared to conventional (e.g. post reactor treatment) methods. The present invention also provides the ability to use a process as disclosed herein as a “plug and play system”, wherein LCBs are generated only when needed, e.g. on existing and already established polymerization systems.

The invention also encompasses a catalyst system suitable for catalyzing the polymerization process for preparing ethylene polymers having long chain branches, comprising a. at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and preferably a bridged metallocene catalyst as defined herein, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I)

Wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and preferably wherein said alkenyl-aluminum compound of formula (I) is as defined herein.

In a preferred embodiment of the invention, a catalyst system is provided wherein said at least one bridged metallocene catalyst is immobilized on an inert support, preferably wherein said inert support is a silica. In a preferred embodiment of the invention, a catalyst system is provided wherein the alkenyl-aluminum compound of formula (I) is not provided on the inert support of the catalyst, or on a support.

In a preferred embodiment of the invention, a catalyst system is provided wherein the alkenyl-aluminum compound of formula (I) is provided as a solution in a diluent (solvent), preferably a hydrocarbon diluent.

The present invention also encompasses ethylene polymers having long chain branches obtained by the process according to the first aspect of the invention or obtained by a process using a catalyst system as provided herein.

The present process brings a solution for the “in-reactor” production of ethylene polymers having long chain branches in a controlled way, e.g. by using one single catalyst system.

The independent and dependent claims set out particular and preferred features of the invention. Features from the dependent claims may be combined with features of the independent or other dependent claims as appropriate.

The present invention will now be further described. In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 represents a ¹ H NMR spectrum (400 MHz, CeDe, 298 K) of Al-octenyl activating agent synthesised according to a Procedure A (formation of side-product).

Figure 2 represents a ¹ H NMR spectrum (400 MHz, CeDe, 298 K) of Al-octenyl activating gent (herein AI-1) synthesised according to a Procedure B (no side-product).

Figure 3 represents a ¹³ C{ ¹ H} NMR spectrum (125 MHz, trichlorobenzene/CeDe, 433 K) of an LCB-branched PE (see Table 1 , entry 1).

Figure 4 represents a ¹³ C{ ¹ H} NMR spectrum (125 MHz, trichlorobenzene/CeDe, 433 K) of an PE prepared in Table 3, entry 3.

Figure 5 represents a ¹³ C{ ¹ H} NMR spectrum (125 MHz, trichlorobenzene/CeDe, 433 K) of a PE prepared in Table 3, entry 4.

Figure 6 represents a dlog |r|*|/dlog co vs. 5 plot of the data series for entries PE5 to PE14.

Figure 7 represents a dlog|r|*|/dlog co vs. 5 plot of the data series for entry PE15 to PE22. Figure 8 represents the first three ethylene insertions with a rac-{EBTHI}Zr catalyst as explained in example 4.

Figure 9 represents a first insertion of ethylene whilst the co-catalyst (herein also activating agent) still remains coordinated to the catalyst rather than dissociate away. Agostic interaction between the co-catalyst and catalyst systems is noted.

Figure 10 represents a second insertion of ethylene as explained in example 4, whereby a dissociation of the co-catalyst enables an ethylene insertion before re-coordination forms a thermodynamically stable bimetallic species.

Figure 11 represents a third insertion of ethylene as explained in example 4, whereby a dissociation of the co-catalyst enables an ethylene insertion. Note the re-formation of a bimetallic species is thermodynamically the most favourable.

Figure 12 represents internal cyclisation and subsequent insertion of ethylene into its cyclic product. Note that this compared to insertions on a linear zirconium species is less favoured because of the kinetic demand needed for an internal cyclisation.

Figure 13 represents the comparison between a first insertion of ethylene and a 1 ,2-vinyl coordination/insertion to the active rac-{EBTHI}Zr catalyst.

Figure 14 represents the comparison between a second insertion of ethylene and a 1 ,2- vinyl coordination/insertion to the active rac-{EBTHI}Zr catalyst.

Figure 15 represents two procedures as applied in the examples to synthesise an alkenylaluminum compound as used in the present invention.

Figure 16 represents rheological properties of PE samples obtained with Zr-1/MAO/AI-1 systems as reported in example 2 wherein Fig. 16(a) represents complex viscosity (|n*l) vs angular frequency (co) plot; and Fig. 16(b) represents a van Gurp-Palmen plot. Shear strain (y) 10%, angular frequencies (co) from 0.1 to 250 rad s ^-1 , T = 190°C.

Figure 17 represents rheological properties of PEs obtained with supp-Zr-1/TIBAL/AI-1 systems as reported in example 3 wherein Fig. 17(a, b) show a complex viscosity (|n*l) vs angular frequency (co plot, and wherein Fig. 17 (c, d) show van Gurp-Palmen plot. Shear strain (y) 10%, angular frequencies (co) from 0.1 to 250 rad s ^-1 , T = 190 °C.

Figure 18 represents Van Gurp-Palmen plot of PEs obtained with supp-rac- {EBTHI}ZrCl2/TIBAL/AI-1 system with different amounts of H2 (as described in example 3). Shear strain (y) 10%, angular frequencies (co) from 0.1 to 250 rad s ^-1 , T = 190°C.

Figure 19 provides an outline of the stepwise protocol applied to gain further insights into possible mechanisms of branching in polyethylene. Figure 20 shows isomers of Al/Zr heterobimetallic intermediates obtained upon coordination of AI-1 (activating agent) to [rac-{EBTHI}ZrMe] ⁺ . Each isomer can be considered a rotamer with respect to the positioning of the alkyl and alkenyl chains.

Figure 21 illustrates an energy profile for the coordination of AI-1 (activating agent) to [rac-{EBTHI}ZrMe] ⁺ followed by the insertion of ethylene via a dissociative pathway. The re-coordination of the co-catalyst (activating agent) species is shown, forming the thermodynamically stable [rac-{EBTHI}Zr(nPr)] ⁺ .

Figure 22 shows dissociation of AI-1 respective of: Al— alkyl (1) or (2) AI-(oct-7-en-1-yl) bond cleavage. It is noted that the latter mechanism involves the transmetallation of the alkyl and alkenyl chains between Al and Zr centers.

Figure 23 illustrates a profile for an insertion of ethylene monomer to [rac-{EBTHI}Zr-(oct- 7-en-1-yl)] ⁺ formed via the cleavage of the Al-alkenyl bond and subsequent oct-7-en-1-yl group transfer. Note, the adduct-less interaction of the monomer suggests a more rapid insertion of ethylene.

Figure 24 shows a two-step mechanism for the re-coordination and insertion of a vinyl group from the AI-1 activating agent.

Figure 25 shows a comparison between the coordination/insertion of ethylene vs. a vinyl group coordination/insertion at the third insertion step. The initial difference in adduct stability is noted.

Figure 26 illustrates transition state geometries for a first ethylene insertion: (top) dissociation of AI-1 agent prior to ethylene insertion, (bottom) non-dissociative transition state.

Figure 27 represents a van Gurp-Palmen plot (phase angle versus complex shear modulus) of ethylene resins (CR1 and Runs 1 to 5) as prepared according to example 7.

Figure 28 represents GPC profiles of ethylene resins (CR1 and Runs 1 to 5) as prepared according to example 7.

Figure 29 represents a van Gurp-Palmen plot (phase angle versus complex shear modulus) of ethylene resins (CR2 and Runs 6 to 10) as prepared according to example 7.

Figure 30 represents a van Gurp-Palmen plot (phase angle versus complex shear modulus) of ethylene resins as prepared according to example 8.

Figure 31 represents a van Gurp-Palmen plot (phase angle versus complex shear modulus) of ethylene resins as prepared according to example 9. DETAILED DESCRIPTION OF THE INVENTION

When describing the invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.

As used herein, the singular forms "a", "an", and "the" include both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a resin" means one resin or more than one resin.

The terms "comprising", "comprises" and "comprised of" as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms "comprising", "comprises" and "comprised of" as used herein comprise the terms "consisting of", "consists" and "consists of".

The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1 .0 to 5.0 includes both 1 .0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

All references cited in the present specification are hereby incorporated by reference in their entirety. In particular, the teachings of all references herein specifically referred to are incorporated by reference.

Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art.

Preferred statements (features) and embodiments, resins and uses of this invention are set herein below. Each statement and embodiment of the invention so defined may be combined with any other statement and/or embodiment unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features or statements indicated as being preferred or advantageous. Hereto, the present invention is in particular captured by any one or any combination of one or more of the below numbered aspects and embodiments, with any other statement and/or embodiment.

1. A process for preparing ethylene polymers having long chain branches, said process comprising the steps of feeding into at least one reactor ethylene monomer and optionally one or more alpha-olefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and optionally one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30 and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm.

2. Process for preparing ethylene polymers having long chain branches, said process comprising the steps of feeding into at least one reactor ethylene monomer and optionally one or more alphaolefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and optionally one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is not immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm. A process for preparing ethylene polymers having long chain branches, said process comprising the steps of feeding into at least one reactor ethylene monomer and optionally one or more alpha-olefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and optionally one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent. A process for preparing ethylene polymers having long chain branches, said process comprising the steps of feeding into at least one reactor ethylene monomer and optionally one or more alpha-olefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and optionally one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent. Process according to any one of statements 1 to 4, wherein the alkenyl-aluminum compound of formula (I) is applied during said polymerization process at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm. Process according to any one of statements 1 to 5, for preparing ethylene polymers having long chain branches, wherein said polymerisation process is a homopolymerisation process comprising the steps of feeding into at least one reactor ethylene monomer, a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula Al R ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent. Process according to any one of statements 1 to 6, wherein said polymerisation process is a homopolymerisation process of said ethylene monomer in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and preferably at a concentration comprised between 10 and 3000 ppm, or between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm. Process according to any one of statements 1 to 5, for preparing ethylene polymers having long chain branches, wherein said polymerisation process is a copolymerisation process, said process comprising the steps of feeding into at least one reactor ethylene monomer and one or more alpha-olefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent. Process according to any one of statements 1 to 5 and 8, wherein said polymerisation process is a copolymerisation process of said ethylene monomer and said one or more alpha-olefins comonomer(s) in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, and wherein said alkenyl-aluminum compound of formula (I) is applied during said copolymerisation process at a concentration of at most 1000 ppm, and preferably at a concentration comprised between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm. Process according to any one of statements 1 and 3 to 9, wherein said at least one bridged metallocene catalyst is immobilized on an inert support. Process according to any one of statements 1 and 3 to 10, wherein said process comprises the step of polymerizing the ethylene monomer and optionally one or more alpha-olefins comonomer(s), under slurry conditions in said at least one reactor in the presence of said catalyst system, a hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum of formula AIR ^b _x . Process according to any one of statements 1 , 3-7, 10-11 , wherein said process comprises the step of homopolymerizing the ethylene monomer under slurry conditions in said at least one reactor in the presence of said catalyst system, a hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum of formula AIR ^b _x . Process according to any one of statements 1 and 3-5, 8-11 , wherein said process comprises the step of copolymerizing the ethylene monomer and one or more alpha-olefins comonomer(s), under slurry conditions in said at least one reactor in the presence of said catalyst system, a hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum of formula AIR ^b _x . Process according to any one of statements 1 to 10, wherein said polymerisation is carried out in gas phase. Process according to any one of statements 1 to 14, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I), wherein each R ¹ is a C1-C20 alkyl, preferably a C1-C10 alkyl, and more preferably is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, and iso-butyl. Process according to any one of statements 1 to 15, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I) wherein R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is hydrogen and m is an integer selected from 1 to 10, and preferably from 4 to 9. Process according to any one of statements 1 to 16, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I) wherein n is an integer or a non-integer from 0.1 to 2.9, or from 0.3 to 2.8 or from 0.5 to 2.7, or from 1 to 2.6, or from 1.1 to 2.6, or from 1.5 to 2.5. Process according to any one of statements 1 to 17, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I) wherein n is selected from the group consisting of 0.5, 0.7, 0.9, 1 , 1.1 , 1.3, 1.5, 1.7 and 2. Process according to any one of statements 1 to 18, wherein said at least one alkenyl- aluminum compound of formula (I) is selected from the group consisting of methyl-di(oct- 7-en-1-yl)aluminum, ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum, isobutyl-di(dec-8- en-1-yl)aluminum, isobutyl-di(dodec-10-en-1-yl)aluminum, dimethyl(oct-7-en-1- yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-8- en-1-yl)aluminum, and diisobutyl(dodec-10-en-1-yl)aluminum, (isobutyl)o.s(oct-7-en-1- yl)2.5aluminum (O^.sAl'Buo.s), (isobutyl)i.i(oct-7-en-1-yl)i.9aluminum (Octi.gAl'Bui.i), and (isobuty I) 1 5(oct-7-en-1 -y I) 1. saluminum (Octi sAl'Bui .5). Process according to any one of statements 1 to 19, wherein the alkenyl-aluminum compound of formula (I) is applied during said polymerization process at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm, or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm. Process according to any one of statements 1 to 20, wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a homogenous solution in a diluent, preferably a hydrocarbon diluent. Process according to any one of statements 1 to 21 , wherein said alkenyl-aluminum compound of formula (I) is not provided on a support. Process according to any one of statements 1 to 22, wherein the at least one bridged metallocene catalyst is a compound according to formula (II):

R ⁴ (Ar) ₂ M ¹ Q ¹ ₂ (II), wherein said metallocene catalyst according to formula (II) has two Ar bound to M ¹ , wherein M ¹ is a transition metal selected from the group consisting of titanium, zirconium, hafnium, and vanadium; and preferably is zirconium; wherein Ar is an aromatic ring, group or moiety and wherein each Ar is independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, and fluorenyl, and preferably from the group consisting of indenyl and tetrahydroindenyl, wherein each of said groups may be optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms, and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P; wherein each Q ¹ is independently selected from the group consisting of halogen, alkyl, heteroalkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, cycloalkoxy, aralkoxy, -COOR ⁶ wherein R ⁶ is hydrogen or alkyl, -N(R ⁷ )2 wherein R ⁷ is selected from the group consisting of hydrogen, alkyl and COR ⁸ wherein R ⁸ is alkyl, and -CO-(NR ⁹ )2 wherein R ⁹ is H or alkyl, and wherein R ⁴ is a structural bridge between the two Ar groups and is selected from the group consisting of C1-C20 alkylene, dialkyl germanium, silicon, siloxane, alkylphosphine, and an amine, and wherein said R ⁴ is optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms, and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P. Process according to any one of statements 1 to 23, wherein said bridged metallocene catalyst is a compound of formula (II),

R ⁴ (Ar) ₂ M ¹ Q ¹ ₂ (II), wherein said metallocene catalyst according to formula (II) has two Ar bound to M ¹ , wherein M ¹ is a transition metal selected from the group consisting of titanium, zirconium, hafnium, and vanadium, and preferably is zirconium, wherein each Ar is independently selected from the group consisting of indenyl, and tetrahydroindenyl, wherein each of said groups may be optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms, and wherein each Q ¹ is independently selected from the group consisting of halogen, alkyl, heteroalkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, cycloalkoxy, aralkoxy, -COOR ⁶ wherein R ⁶ is hydrogen or alkyl, -N(R ⁷ )2 wherein R ⁷ is selected from the group consisting of hydrogen, alkyl and COR ⁸ wherein R ⁸ is alkyl, and -CO-(NR ⁹ )2 wherein R ⁹ is H or alkyl, and wherein R ⁴ is a structural bridge between the two Ar groups and selected from the group consisting of C1-C20 alkylene and silicon, and wherein said R ⁴ is optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms. Process according to any one of statements 1 to 24, wherein said bridged metallocene catalyst is a compound of formula (II),

R ⁴ (Ar) ₂ M ¹ Q ¹ ₂ (II), wherein said metallocene catalyst according to formula (II) has two Ar bound to M ¹ , wherein M ¹ is zirconium, wherein each Q ¹ is a halogen, wherein each Ar is an indenyl or tetrahydroindenyl, wherein each of said Ar group may be optionally substituted with one or more substituents each independently selected from the group consisting of halogen and a hydrocarbyl having 1 to 20 carbon atoms, and wherein R ⁴ is a structural bridge between the two Ar groups and is selected from the group consisting of C1-C20 alkylene and silicon, and wherein said R ⁴ is substituted with one or more substituents each independently selected from the group consisting of halogen and a hydrocarbyl having 1 to 20 carbon. Process according to any one of statements 1 to 25, wherein said bridged metallocene catalyst is a compound of formula (II),

R ⁴ (Ar) ₂ M ¹ Q ¹ ₂ (II), wherein said metallocene catalyst according to formula (II) has two Ar bound to M ¹ , wherein M ¹ is zirconium, wherein each Q ¹ is a halogen, preferably chlorine or fluorine, wherein each Ar is a tetrahydroindenyl, wherein each of said Ar group may be optionally substituted with one or more substituents each independently selected from halogen or from the group consisting of linear or branched Ci-C2oalkyl; C3- C2ocycloalkyl; Cs-C2oaryl; Ce-C2oalkylaryl; Ce-C2oarylalkyl, and any combinations thereof, and wherein R ⁴ is a divalent group or moiety bridging the two tetrahydroindenyls and is selected from the group consisting of C1-C4 alkylene and silicon, and wherein said R ⁴ is optionally substituted with one or more substituents each independently selected from halogen or from the group consisting of linear or branched Ci-C2oalkyl; C3- C2ocycloalkyl; Cs-C2oaryl; Ce-C2oalkylaryl; Ce-C2oarylalkyl, and any combinations thereof. Process according to any one of statements 1 to 26, wherein said bridged metallocene catalyst is a compound of formula (II):

R ⁴ (Ar) ₂ M ¹ Q ¹ ₂ (II), wherein said metallocene catalyst according to formula (II) has two Ar bound to M ¹ , wherein M ¹ is zirconium, wherein each Q ¹ is independently chlorine or fluorine, wherein each Ar is a tetrahydroindenyl, wherein each of said Ar group may be optionally substituted with one or more substituents each independently selected from the group consisting of linear or branched Ci-C2oalkyl; C3-C2ocycloalkyl; Cs-C2oaryl; Ce- C2oalkylaryl; Ce-C2oarylalkyl, and any combinations thereof, and wherein R ⁴ is a divalent group or moiety bridging the two tetrahydroindenyls and is a C1-C4 alkylene, preferably methylene or ethylene, and wherein said R ⁴ is optionally substituted with one or more substituents each independently selected from the group consisting of linear or branched Ci-C2oalkyl; C3-C2ocycloalkyl; Cs-C2oaryl; Ce- C2oalkylaryl; Ce-C2oarylalkyl, and any combinations thereof. Process according to any one of statements 1 to 27, wherein said alkylaluminum of formula AIR ^b _x is trialkylaluminum. Process according to any one of statements 1 to 28, wherein said alkylaluminum of formula AIR ^b _x is selected from the group comprising Tri-/so-Butyl Aluminum (Tl BAI), Tri- Ethyl Aluminum (TEAI), Tri-Methyl Aluminum (TMA), and dimethyl-Ethyl Aluminum , and preferably is TIBAI or TEAI. Process according to any one of statements 1 to 29, wherein the weight ratio of said activating agent to said alkylaluminum of formula AIR ^b _x is ranging from 10/90 to 90/10, preferably from 25/75 to 90/10, more preferably from 50/50 to 90/10. Process according to any one of statements 1 and 3 to 30, wherein said inert support is a silica. Process according to any one of statements 1 and 3 to 31 , wherein said inert support is a silica support, with the proviso that said silica support is not an ion-exchange layered silica. Process according to any one of statements 1 to 5 and 8 to 32, wherein the one or more alpha-olefins comonomers are selected from the group comprising propylene, 1- butene, 1 -pentene, 1 -hexene and 1 -octene, and preferably said comonomer is 1- hexene. Process according to any one of statements 1 to 33, wherein said hydrogen is applied during said polymerization process at a concentration of below 5000 ppm, such as below 3000 ppm, such as below 2500 ppm, such as between 10 and 1000 ppm, such as between 100 and 850 ppm. Process according to any one of statements 1 to 34, wherein said polymerization step is carried out in one or more reactors preferably selected from continuous stirred-tank reactor, loop reactor, gas phase, or autoclave. Process according to any one of statements 1 to 35, wherein said process is carried out in one single reactor. Process according to any one of statements 1 to 35, wherein said process is carried out in two or more reactors, connected in series. Process according to any one of statements 1 to 35, wherein said process is carried out in a double loop reactor. Process according to any one of statements 1 to 38, wherein said ethylene polymer has a rheology long chain branching index (g _r heo) lower than 0.90, preferably lower than 0.80, preferably lower than 0.75, preferably lower than 0.70, preferably lower than 0.65, preferably lower than 0.60, preferably lower than 0.55, as determined by the method disclosed in the example section. Process according to any one of statements 1 to 39, wherein said ethylene polymer has a rheology long chain branching index (g _r heo) higher than 0.20, or higher than 0.25, or higher than 0.30, or higher than 0.35, or higher than 0.40, as determined by the method disclosed in the example section. A catalyst system suitable for catalyzing the polymerization process for preparing ethylene polymers having long chain branches, comprising a. at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30. A catalyst system suitable for catalyzing the polymerization process for preparing ethylene polymers having long chain branches, comprising a. at least one bridged metallocene catalyst which is immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I)

Wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30. A catalyst system suitable for catalyzing the polymerization process for preparing ethylene polymers having long chain branches, comprising a. at least one bridged metallocene catalyst which is not immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30. Catalyst system according to any one of statements 41 and 42, wherein the alkenylaluminum compound of formula (I) is not provided on the inert support of the catalyst. Catalyst system according to any one of statements 41 to 44, wherein the alkenylaluminum compound of formula (I) is not provided on a support. Catalyst system according to any one of statements 41 to 45, wherein the alkenylaluminum compound of formula (I) is provided as a solution in a diluent (solvent), preferably a hydrocarbon diluent. Catalyst system according to any one of statements 41 to 46 wherein said bridged metallocene catalyst is as defined in any of one of statements 1 , 23-27. Catalyst system according to any of statements 41 to 47, wherein said alkenylaluminum compound of formula (I) is as defined in any one of statements 1-22. Catalyst system according to any one of statements 41-42 and 44-48, wherein said inert support is a silica. Catalyst system according to any one of statements 41-42 and 44-49, wherein said inert support is a silica, with the proviso that said silica support is not an ion-exchange layered silica. Use of a catalyst system according to any one of statements 41 to 50 in a process for preparing ethylene polymers having long chain branches. Use of a catalyst system according to any one of statements 41-42 and 44-50 in a process for preparing ethylene polymers having long chain branches as defined in any one of statements 1 and 3 to 40. Use of a catalyst system according to any one of statements 41 , 43, and 45-48 in a process for preparing ethylene polymers having long chain branches as defined in any one of statements 2-3, 5-9, 14-40. Ethylene polymer having long chain branches obtained by a process according to any one of statements 1 to 40 or obtained by a process using a catalyst system according to any one of statements 41 to 50. Ethylene polymer having long chain branches according to statement 54, wherein said ethylene polymer has a rheology long chain branching index (g _r heo) lower than 0.90, preferably lower than 0.80, preferably lower than 0.75, preferably lower than 0.70, preferably lower than 0.65, preferably lower than 0.60, preferably lower than 0.55, as determined by the method disclosed in the example section. Ethylene polymer having long chain branches according to statement 54 or 55, wherein said ethylene polymer has a rheology long chain branching index (g _r heo) higher than 0.20, or higher than 0.25, or higher than 0.30, or higher than 0.35, or higher than 0.40, as determined by the method disclosed in the example section. Ethylene polymer having long chain branches according to any one of statements 54 to 56, wherein said ethylene has a MI2, as determined according to ISO 1133:2005 Method B, condition D, at a temperature 190°C, and a 2.16 kg load using a die of 2.096 mm, up to 50 g/10min, preferably comprised between 0.1 and 25 g/10min, or between 0.1 and 20 g/10min. Ethylene polymer having long chain branches according to any one of statements 54 to 57, wherein said ethylene has a HLMI, as determined according to ISO 1133:2005 Method B, condition G, at a temperature 190°C, and a 21.6 kg load using a die of 2.096 mm, up to 150 g/10min, such as between 1 and 100 g/10min, or between 5 and 80 g/10min. Ethylene polymer having long chain branches according to any one of statements 54 to 58, wherein said ethylene polymer has a ratio of weight average molecular weight (M _w ) to number average molecular weight (M _n ) [M _w /M _n ] of at most 4.5, at most 4.0 or at most 3.8, or at most 3.6. Ethylene polymer having long chain branches according to any one of statements 54 to 59, wherein said ethylene polymer has a ratio of weight average molecular weight (M _w ) to number average molecular weight (M _n ) [M _w /M _n ] of at least 2.0, preferably at least 2.2, preferably at least 2.3, preferably at least 2.4, preferably at least 2.5, preferably at least 2.6, preferably at least 2.7, preferably at least 2.8, preferably at least 2.9, preferably at least 3.0. Use of an alkenyl-aluminum compound of formula (I) as defined in any one of statements 1-22, as activating agent in a polymerization process, preferably a slurry polymerization process, for preparing ethylene polymers having long chain branches, wherein said compound is used in combination with at least one bridged metallocene catalyst which is preferably immobilized on an inert support, preferably a silica support, and preferably at least one bridged metallocene catalyst as defined in in any one of statements 1 , 23-27. Use according to statement 61 , for preparing ethylene polymer having long chain branches, preferably ethylene polymer as defined in any one of statements 54 to 60. Use according to any of statements 61 to 62, wherein said alkenyl-aluminum compound of formula (I) is used during said polymerization at a concentration of at most 3000 ppm, or at most 2000 ppm, or at most 1000 ppm, or at most 750 ppm, or at most 600 ppm, or at most 500 ppm, or most 400 ppm, or at most 350 ppm. Use according to any one of statements 61 to 63, wherein said alkenyl-aluminum compound of formula (I) is used during polymerisation at a concentration of at least 10 ppm, such as at least 15 ppm, such as at least 20 ppm. Use according to any one of statements 61 to 64, wherein said alkenyl-aluminum compound of formula (I) is used said polymerization process at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm. Use according to any one of statements 61 to 65, wherein alkenyl-aluminum compound of formula (I) is used in a slurry polymerisation process for preparing ethylene polymers having long chain branches. Use according to any one of statements 61 to 65, wherein alkenyl-aluminum compound of formula (I) is used in in a gas phase polymerisation process for preparing ethylene polymers having long chain branches. Use according to any one of statements 61 to 67, wherein said alkenyl-aluminum compound of formula (I) is not provided on said inert support or on a support. 69. Use according to any one of statements 61 to 68, wherein said alkenyl-aluminum compound of formula (I) is used as a homogenous solution in a diluent, preferably a hydrocarbon diluent.

70. Use according to any one of statements 61 to 69, wherein said alkenyl-aluminum compound of formula (I) is used a homopolymerisation process as defined in any one of statements 1 to 7 and 10 to 40 at a concentration of at most 3500 ppm, and preferably at a concentration comprised between 10 and 3000 ppm, or between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

71. Use according to any one of statements 61 to 69, wherein said alkenyl-aluminum compound of formula (I) is used a copolymerisation process as defined in any one of statements 1 to 5 and 8 to 40 at a concentration of at most 1000 ppm, and preferably at a concentration comprised between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

72. An article made of an ethylene polymer according to any one of statements 54 to 60.

The present invention provides a process for preparing ethylene polymers having long chain branches. Long Chain Branches (LCBs) are ramifications in the linear structures of polymers. They differ from Short Chain Branches (SCBs) by their length (typically less than 40 carbons to longer than the average critical entanglement distance) and by how they affect rheological properties of the polymer. Whereas SCBs influence thermal and mechanical properties, LCBs modify the melt rheological behaviour, increasing for example the melt strength of the polymer.

In virtue of their intrinsic nature, metallocenes are able to produce some LCBs, while ZN catalyst generally aren’t. The inventors have now shown that the generation of LCBs can be further fined-tuned and/or steered by the use of an alkenyl-aluminum compound, as defined herein, during polymerisation.

The present invention provides ethylene polymers having long chain branches. The terms “ethylene polymer”, “ethylene polymers”, “PE” or “polyethylene” as used herein are synonymous and may be used interchangeably.

The terms “ethylene polymer” or “polyethylene” may in certain embodiments encompasses copolymers of ethylene and one or more alpha-olefins as defined herein.

The present invention provides a process for preparing polyethylene having long chain branches comprising the steps of feeding into at least one reactor ethylene monomer and optionally one or more alphaolefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and optionally one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30 and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl- aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent.

The present invention also provides a process for preparing polyethylene having long chain branches comprising the steps of feeding into at least one reactor ethylene monomer and optionally one or more alphaolefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and optionally one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is not immobilized on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl- aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent.

The term "metallocene catalyst" is used herein to describe any transition metal complexes comprising metal atoms bonded to one or more ligands. The metallocene catalysts are compounds of Group IV transition metals of the Periodic Table such as titanium, zirconium, hafnium, etc., and have a coordinated structure with a metal compound and ligands composed of one or two groups of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl or their derivatives. The structure and geometry of the metallocene can be varied to adapt to the specific need of the producer depending on the desired polymer. Metallocenes comprise a single metal site, which allows for more control of branching and molecular weight distribution of the polymer. Monomers are inserted between the metal and the growing chain of polymer. Specifically, for this invention the catalyst needs to be a “bridged metallocene catalyst”.

In one embodiment the bridged metallocene catalyst can be represented by formula (II):

R ⁴ (Ar) ₂ M ¹ Q ¹ ₂ (II), wherein said metallocene catalyst according to formula (II) has two Ar bound to M ¹ , wherein M ¹ is a transition metal selected from the group consisting of titanium, zirconium, hafnium, and vanadium; wherein Ar is an aromatic ring, group or moiety and wherein each Ar is independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, and fluorenyl, wherein each of said groups may be optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms, and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P; wherein each Q ¹ is independently selected from the group consisting of halogen, alkyl, heteroalkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, cycloalkoxy, aralkoxy, -COOR ⁶ wherein R ⁶ is hydrogen or alkyl, -N(R ⁷ )2 wherein R ⁷ is selected from the group consisting of hydrogen, alkyl and COR ⁸ wherein R ⁸ is alkyl, and -CO-(NR ⁹ )2 wherein R ⁹ is H or alkyl, and wherein R ⁴ is a structural bridge between the two Ar groups and is selected from the group consisting of C1-C20 alkylene, dialkyl germanium, silicon, siloxane, alkylphosphine, and an amine, and wherein said R ⁴ is optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms, and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P.

In some preferred embodiments, the bridged metallocene catalyst as used herein is represented by formula (II), wherein each Ar is independently selected from the group consisting of indenyl and tetrahydroindenyl. Preferably, said bridged metallocene catalyst comprises a bridged bis(indenyl) and/or a bridged bis(tetrahydrogenated indenyl) component. Most preferably said bridged metallocene catalyst comprises a bridged bis(tetrahydroindenyl) component.

In more preferred embodiments, the metallocene catalyst is a bridged metallocene catalyst of formula (II):

R ⁴ (Ar) ₂ M ¹ Q ¹ ₂ (II), wherein said metallocene catalyst according to formula (II) has two Ar bound to M ¹ , wherein M ¹ is a transition metal selected from the group consisting of titanium, zirconium, hafnium, and vanadium, and preferably is zirconium, wherein each Ar is independently selected from the group consisting of indenyl, and tetrahydroindenyl, and preferably tetrahydroindenyl, wherein each of said groups may be optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms, and wherein each Q ¹ is independently selected from the group consisting of halogen, alkyl, heteroalkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, cycloalkoxy, aralkoxy, -COOR ⁶ wherein R ⁶ is hydrogen or alkyl, -N(R ⁷ )2 wherein R ⁷ is selected from the group consisting of hydrogen, alkyl and COR ⁸ wherein R ⁸ is alkyl, and -CO-(NR ⁹ )2 wherein R ⁹ is H or alkyl, and wherein R ⁴ is a structural bridge between the two Ar groups and selected from the group consisting of C1-C20 alkylene and silicon, and preferably C1-C20 alkylene, and wherein said R ⁴ is optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, SiR ⁵ 3 wherein R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms, and a hydrocarbyl having 1 to 20 carbon atoms.

Each tetrahydroindenyl component may optionally be substituted in the same way or differently from one another at one or more positions of either of the fused rings. Each substituent is independently chosen.

As used herein, the term “hydrocarbyl having 1 to 20 carbon atoms” refers to a moiety selected from the group comprising, preferably consisting of, a linear or branched C1-C20 alkyl; C3-C20 cycloalkyl; C5-C20 aryl; C6-C20 alkylaryl and C6-C20 arylalkyl, and any combinations thereof. Exemplary hydrocarbyl groups are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cetyl, cyclopentyl, cyclohexyl, cycloheptyl, 2-ethylhexyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4- methylphenyl, 2-ethylphenyl, 2-tert-butyl phenyl, 3-tert-butylphenyl, 4-tert-butyl phenyl.

As used herein, the term “hydrocarboxy having 1 to 20 carbon atoms” refers to a moiety with the formula hydrocarbyl-O-, wherein the hydrocarbyl has 1 to 20 carbon atoms as described herein. Preferred hydrocarboxy groups are selected from the group comprising alkyloxy, alkenyloxy, cycloalkyloxy or aralkoxy groups.

As used herein, the term “alkyl”, by itself or as part of another substituent, refers to straight or branched saturated hydrocarbon group joined by single carbon-carbon bonds having 1 or more carbon atom, for example 1 to 12 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 6 carbon atoms, for example 1 to 4 carbon atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Alkyl groups have the general formula C _n H2n+i. Preferably n in said general formula C _n H2n+i is an integer of at least 1 , such as from 1 to 20 or from 1 to 12 or from 1 to 10 or from 1 to 6. Thus, for example, Ci-i2alkyl means an alkyl of 1 to 12 carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, ferf-butyl, 2-methylbutyl, pentyl and its chain isomers, hexyl and its chain isomers, heptyl and its chain isomers, octyl and its chain isomers, nonyl and its chain isomers, decyl and its chain isomers, undecyl and its chain isomers, dodecyl and its chain isomers.

The term “heteroalkyl” as a group or part of a group, refers to an acyclic alkyl wherein one or more carbon atoms are replaced by at least one heteroatom selected from the group comprising O, Si, S, B, and P, with the proviso that said chain may not contain two adjacent heteroatoms. This means that one or more -CH3 of said acyclic alkyl can be replaced by -OH for example and/or that one or more -CR2- of said acyclic alkyl can be replaced by O, Si, S, B, and P.

As used herein, the term “cycloalkyl”, by itself or as part of another substituent, refers to a saturated or partially saturated cyclic alkyl radical. Cycloalkyl groups have the general formula C _n H2n-i. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Preferably n in said general formula C _n H2n-i is an integer of at least 3, such as from 3 to 20 or from 3 to 12 or from 3 to 10 or from 3 to 6. Examples of Cs-ecycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

The term “aryl” as used herein by itself or as part of another substituent, refers to an aromatic hydrocarbon of 5-20 carbon atoms derived by the removal of hydrogen from a carbon atom of an aromatic ring system. Examples of aryl groups include, but are not limited to 1 ring, or 2 or 3 rings fused together, of which at least one ring is aromatic. Such ring can be derived from benzene, naphthalene, anthracene, biphenyl, 2,3-dihydro-1 H- indenyl, 5,6,7,8-tetrahydronaphthalenyl, 1 ,2,6,7,8,8a-hexahydroacenaphthylenyl, 1 ,2- dihydroacenaphthylenyl, and the like. Particular aryl groups are phenyl and naphthyl, especially phenyl.

As used herein, the term “arylalkyl”, by itself or as part of another substituent, refers to an alkyl group as defined herein, wherein a hydrogen atom is replaced by an aryl as defined herein. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. The arylalkyl group can comprise 6 to 20 carbon atoms, e.g. the alkyl moiety of the arylalkyl group is 1 to 6 carbon atoms and the aryl moiety is 5 to 14 carbon atoms. Typical arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl, 2- naphthylethyl, and the like. As used herein, the term “alkylaryl”, by itself or as part of another substituent, refers to an aryl group as defined herein, wherein a hydrogen atom is replaced by an alkyl as defined herein. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group or subgroup may contain. The alkylaryl group can comprise 6 to 20 carbon atoms, e.g. the alkyl moiety of the alkylaryl group is 1 to 6 carbon atoms and the aryl moiety is 5 to 14 carbon atoms. Typical alkylaryl groups include, but are not limited to 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2- ethylphenyl, 2-tert-butyl phenyl, 3-tert-butyl phenyl, 4-tert-butylphenyl.

As used herein, the term “alkylene”, by itself or as part of another substituent, refers to alkyl groups that are divalent, i.e., with two single bonds for attachment to two other groups. Alkylene groups may be linear or branched and may be substituted as indicated herein. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, C1-C20 alkylene refers to an alkylene having between 1 and 20 carbon atoms. An alkylene group may be a C1-C20 alkylene, or a C1-C10 alkylene, or a Ci-Ce alkylene or a C1-C4 alkylene. Nonlimiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methyl-ethylene (-CH(CH3)-CH2-), n-propylene (-CH2- CH2-CH2-), 2-methylpropylene (-CH2-CH(CH3)-CH2-), 3-methylpropylene (-CH2-CH2- CH(CH ₃ )-), n-butylene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH(CH ₃ )-CH ₂ - CH2-), 4-methylbutylene (-CH2-CH2-CH2-CH(CH3)-), pentylene and its chain isomers, hexylene and its chain isomers, heptylene and its chain isomers, octylene and its chain isomers, nonylene and its chain isomers, decylene and its chain isomers, undecylene and its chain isomers, dodecylene and its chain isomers.

Exemplary halogen atoms include chlorine, bromine, fluorine and iodine, wherein fluorine and chlorine are preferred.

A preferred example of a bridged metallocene catalyst for use in the present invention is represented by the metallocene catalyst of formula X provided in the example section.

In certain embodiments, bridged metallocene catalysts used herein are not immobilized on a support. In other words, in certain embodiments a homogenous catalyst is used. A bridged metallocene catalyst which is not immobilized on a support is also referred herein to a “non-supported” bridged metallocene catalyst.

The bridged metallocene catalysts used herein are immobilized on a support, more particularly on an inert support. The support can be an inert organic or inorganic solid, which is chemically unreactive with any of the components of the conventional bridged metallocene catalyst. Suitable support materials for the supported catalyst include solid inorganic oxides, such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, as well as mixed oxides of silica and one or more Group 2 or 13 metal oxides, such as silica-magnesia and silica-alumina mixed oxides. Silica, alumina, and mixed oxides of silica and one or more Group 2 or 13 metal oxides are preferred support materials. Preferred examples of such mixed oxides are the silica-aluminas. Most preferred is a silica compound as inert support.

In a preferred embodiment, the bridged metallocene catalyst is provided on a silica support. The silica may be in granular, agglomerated, fumed or other form.

In some embodiments, the support of the bridged metallocene catalyst is a porous support, and preferably a porous silica support having a surface area comprised between 200 and 900 m ² /g.

In another embodiment, the support of the polymerization catalyst is a porous support, and preferably a porous silica support having an average pore volume comprised between 0.5 and 4 ml/g.

In yet another embodiment, the support of the polymerization catalyst is a porous support, and preferably a porous silica support having an average pore diameter comprised between 50 and 300 A, and preferably between 75 and 220 A.

In certain embodiments, a non-supported bridged metallocene catalyst is activated by an additional activating agent. The activating agent can be any activating agent known for this purpose such as an aluminum-containing activating agent, a boron-containing activating agent or a fluorinated activating agent. The aluminum-containing activating agent may comprise an alumoxane, an alkylaluminum, a Lewis acid and/or a fluorinated catalytic support.

Preferably, the supported bridged metallocene catalyst is activated by an additional activating agent. The activating agent can be any activating agent known for this purpose such as an aluminum-containing activating agent, a boron-containing activating agent or a fluorinated activating agent. The aluminum-containing activating agent may comprise an alumoxane, an alkylaluminum, a Lewis acid and/or a fluorinated catalytic support.

In some embodiments, alumoxane is used as an activating agent for the bridged metallocene catalyst. The alumoxane can be used in conjunction with a catalyst in order to improve the activity of the catalyst during the polymerization reaction.

As used herein, the term “alumoxane” and “aluminoxane” are used interchangeably, and refer to a substance, which is capable of activating the bridged metallocene catalyst. In some embodiments, alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes. In a further embodiment, the alumoxane has formula (III) or (IV)

R ^C -(AI(R ^C )-O) _X -AIR ^C 2 (III) for oligomeric, linear alumoxanes; or

(-AI(R ^c )-O-) _y (IV) for oligomeric, cyclic alumoxanes wherein x is 1-40, and preferably 10-20; wherein y is 3-40, and preferably 3-20; and wherein each R ^c is independently selected from a Ci-Csalkyl, and preferably is methyl. In a preferred embodiment, the alumoxane is methylalumoxane (MAO).

In a preferred embodiment, the bridged metallocene catalyst is a supported metallocene -alumoxane catalyst comprising a bridged metallocene catalyst and an alumoxane which are bound on a porous silica support. Preferably, the bridged metallocene catalyst is a bridged bis(indenyl) metallocene catalyst or a bridged bis(tetrahydrogenated indenyl) metallocene catalyst, most preferably a bridged bis(tetrahydrogenated indenyl) metallocene catalyst.

In certain embodiments of the present process a homopolymerisation reaction is carried out. Preferably, a process for preparing ethylene polymers having long chain branches is provided, wherein said polymerisation process is a homopolymerisation process comprising the steps of feeding into at least one reactor ethylene monomer, a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula Al R ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and preferably is immobilised on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ ) _n -AI-(R ² )3-n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent.

Preferably in such embodiments of a homopolymerisation process according to the invention, said ethylene monomer is polymerised in the presence of a catalyst system as defined herein, optional hydrocarbon diluent, optional hydrogen and optional alkylaluminum, and the alkenyl-aluminum compound of formula (I) as defined herein is applied during said polymerisation process at a concentration of at most 3500 ppm, and preferably at a concentration comprised between 10 and 3000 ppm, or between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

In certain embodiments of the present invention, a copolymerisation reaction is carried out.

Preferably, a process for preparing ethylene copolymers having long chain branches is provided, wherein said polymerisation process is a copolymerisation process comprising the steps of feeding into at least one reactor ethylene monomer and one or more alpha-olefins comonomer(s), a catalyst system, optionally a hydrocarbon diluent, optionally hydrogen and optionally an alkylaluminum of formula AIR ^b _x , wherein x is an integer selected from 1 to 3 and each R ^b is independently selected from alkyl, and polymerizing in said at least one reactor, the ethylene monomer and one or more alpha-olefins comonomer(s), in the presence of said catalyst system, said optional hydrocarbon diluent, said optional hydrogen and said optional alkylaluminum, thereby producing ethylene polymers having long chain branches, wherein said catalyst system comprises a. at least one bridged metallocene catalyst which is optionally immobilized on an inert support, and preferably is immobilised on an inert support, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and wherein said alkenyl-aluminum compound of formula (I) is applied during said polymerisation process at a concentration of at most 3500 ppm, and wherein the alkenyl-aluminum compound of formula (I) is injected in said at least one reactor as a solution in a diluent (solvent), preferably a hydrocarbon diluent.

Preferably in such embodiments of a copolymerisation process according to the invention, said ethylene monomer is copolymerised with one or more alpha-olefins comonomer(s) in the presence of said catalyst system as defined herein, optional hydrocarbon diluent, optional hydrogen and optional alkylaluminum, and an alkenyl-aluminum compound of formula (I) as defined herein, is applied during said copolymerisation process at a concentration of at most 1000 ppm, and preferably at a concentration comprised between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

In preferred embodiments of a process of the invention, said alpha-olefin comonomer is selected from the group comprising propylene, 1 -butene, 1 -pentene, 1 -hexene and 1- octene, and preferably said comonomer is 1 -hexene.

According to the present invention, a process for preparing ethylene polymers having long chain branches is provided which is carried out in the presence of a catalyst system comprising a bridged metallocene catalyst and at least one activating agent comprising or consisting of an alkenyl-aluminum compound of formula (I) as defined herein.

In certain embodiments, said alkenyl-aluminum compound is a compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I) wherein n is an integer or a non-integer from 0.1 to 2.9, or from 0.3 to 2.8 or from 0.5 to 2.7, or from 1 to 2.6, or from 1.5 to 2.5. In certain preferred embodiments n is selected from the group consisting of 0.5, 0.7, 0.9, 1 , 1.1 , 1.3, 1.5, 1.7 and 2.

In certain embodiments, said alkenyl-aluminum compound is a compound of formula (I) as given herein, wherein each R ¹ is a C1-C20 alkyl, preferably a C1-C10 alkyl, wherein said alkyl can be branched, linear or cyclic. For example, (each) R ¹ in formula (I) may be independently chosen from the group comprising methyl, ethyl, n-propyl, iso-propyl, n- butyl, iso-butyl, 4-methyl-pentyl, n-hexyl and dodecyl. In certain preferred embodiments, R ¹ is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, and iso-butyl.

In certain embodiments, said alkenyl-aluminum compound is a compound of formula (I) as given herein, wherein (each) R ² is -(CH2)m-CH2-CR ³ =CH2, and wherein R ³ is hydrogen or an alkyl, such as a C1-C20 alkyl, preferably a C1-C10 alkyl, wherein said alkyl can be branched or linear. In certain preferred embodiments R ² is -(CH2)m-CH2-CR ³ =CH2, wherein m is an integer selected from 1 to 30, preferably from 1 to 20, preferably from 1 to 10 preferably from 4 to 9, and wherein R ³ is hydrogen.

Examples of a suitable alkenyl-aluminum compound of formula (I) for use in a catalyst system as defined herein may be selected from the group comprising but not limited to methyl-di(oct-7-en-1-yl)aluminum, ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1- yl)aluminum, isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum, isobutyl-di(dec-8-en-1-yl)aluminum, isobutyl-di(dodec-10-en-1-yl)aluminum, dimethyl(oct- 7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-8- en-1-yl)aluminum, and diisobutyl(dodec-10-en-1-yl)aluminum, (isobutyl)o.5(oct-7-en-1- yl)2.5aluminum (Oct2.5AI'Buo.5), (isobutyl)i.i(oct-7-en-1-yl)i.9aluminum (Octi.gAl'Bui.i), (isobutyl)i.3(oct-7-en-1-yl)i.7aluminum (OctuAl'Bui.s), and (isobutyl)i.5(oct-7-en-1- yl)i.5aluminum (Octi.sAl'Bui.s).

In certain embodiments of the catalyst system, the bridged metallocene catalyst is not immobilised on an inert support. In other words, in certain embodiments a homogenous catalyst system is used.

In preferred embodiments of the catalyst system, the bridged metallocene catalyst is immobilised on an inert support, preferably a silica support, while the alkenyl-aluminum compound of formula (I) is separately provided; and is not provided on a support or on said inert support. In certain embodiments, the alkenyl-aluminum compound of formula (I) is used as a solution in a diluent (solvent), preferably as a homogenous solution in a diluent, preferably a hydrocarbon diluent as described herein. Non-limiting illustrative examples of suitable diluents are n-butane, isobutane, n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, cycloheptane, methylcyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylenes, chloroform, chloroarenes such as chlorobenzene, tetrachloroethylene, dichloroethane and trichloroethane.

In certain embodiments, an alkenyl-aluminum compound of formula (I) as defined herein is applied in a polymerisation process as described herein, at a concentration of at most 3500 ppm, and preferably at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm, or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

Therefore, the present invention also relates to the use of an alkenyl-aluminum compound of formula (I) as defined herein in a polymerization process for making ethylene polymers having long chain branches, preferably at a concentration of at most 3500 ppm, such as at most 3000 ppm, or at most 2000 ppm, or at most 1000 ppm, or at most 750 ppm, or at most 600 ppm, or at most 500 ppm.

In certain preferred embodiments, said alkenyl-aluminum compound of formula (I) as defined herein is used in said polymerization process at a concentration of at least 10 ppm, such as at least 15 ppm, or at least 20 ppm.

In certain preferred embodiments, said an alkenyl-aluminum compound of formula (I) as defined herein is used in said polymerization process at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm, or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

In certain embodiments, an alkenyl-aluminum compound of formula (I) as defined herein is applied in an ethylene homopolymerisation process as described herein, at a concentration of at most 3500 ppm, and preferably at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm, or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

In certain embodiments, an alkenyl-aluminum compound of formula (I) as defined herein is applied in a copolymerisation process of ethylene as described herein, at a concentration of at most 1000 ppm, and preferably at a concentration comprised between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

Said alkenyl-aluminum compound of formula (I) as defined herein wherein can be used in a slurry or gas phase polymerization processes; preferably in slurry polymerization processes for preparing ethylene polymers having long chain branches, such as those defined herein.

According to the present invention, a process for preparing polyethylene having long chain branches is provided which is performed in the presence of a catalyst system comprising a bridged metallocene catalyst and an alkenyl-aluminum compound of formula (I) as defined herein, further in the presence of an alkylaluminum of formula AIR ^b _x , wherein each R ^b is independently selected from alkyl preferably an alkyl having from 1 to 12 carbon atoms, and wherein x is an integer selected from 1 to 3. Non-limiting examples are Tri- /so-Butyl Aluminum (TIBAL), Tri-Ethyl Aluminum (TEAL), Tri-Methyl Aluminum (TMA), and Dimethyl-Ethyl Aluminum. Especially suitable are trialkylaluminums, the most preferred being Tri-/so-Butyl Aluminum (TIBAL) and Tri-Ethyl Aluminum (TEAL).

In certain embodiment, the process is performed in the presence of an alkenyl-aluminum compound of formula (I) and an alkylaluminum of formula AIR ^b _x , in a weight ratio of compound of formula (I) I alkylaluminum ranging from 10/90 to 90/10. By varying the ratio between these two values, the amount of long chain branching can be shifted and finetuned towards a certain desired value. In a more preferred embodiment, the process is performed in the presence of a compound of formula (I) and an alkylaluminum of formula AIR ^b _x in a weight ratio of said compound of formula (I) /alkylaluminum of formula AIR ^b _x ranging from 25/75 to 90/10, preferably ranging from 50/50 to 90/10.

In certain preferred embodiments, the process is performed in the presence of alkenyl- aluminum compound of formula (I) and TIBAI in a weight ratio of compound of formula (I) I TIBAI ranging from 10/90 to 90/10. In a more preferred embodiment, the process is performed in the presence of a compound of formula (I) and TIBAI in a weight ratio of said compound of formula (I) / Tl BAI ranging from 25/75 to 90/10, preferably ranging from 50/50 to 90/10.

In certain preferred embodiments, the process is performed in the presence of alkenyl- aluminum compound of formula (I) and TEAI in a weight ratio of compound of formula (I) I TEAI ranging from 10/90 to 90/10. In a more preferred embodiment, the process is performed in the presence of a compound of formula (I) and TEAI in a weight ratio of said compound of formula (I) I TEAI ranging from 25/75 to 90/10, preferably ranging from 50/50 to 90/10. A polymerization process for preparing polyethylene having long chain branches according to the present invention may be carried out in a slurry, optionally in the presence of a hydrocarbon diluent or in gas phase, preferably in a slurry.

Diluents or hydrocarbon diluents which are suitable for being used in accordance with the present invention are preferably liquid hydrocarbon diluents which may comprise but are not limited to hydrocarbon diluents such as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents, or halogenated versions of such solvents. The preferred solvents are C12 or lower, straight chain or branched chain, saturated hydrocarbons, C5 to C9 saturated alicyclic or aromatic hydrocarbons or C2 to C6 halogenated hydrocarbons. Nonlimiting illustrative examples of solvents are n-butane, isobutane, n-pentane, n-hexane, n- heptane, cyclopentane, cyclohexane, cycloheptane, methylcyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylenes, chloroform, chloroarenes such as chlorobenzene, tetrachloroethylene, dichloroethane and trichloroethane. In a preferred embodiment of the present invention, said diluent is isobutane. However, it should be clear from the present invention that other diluents may as well be applied according to the present invention.

The step of polymerizing or copolymerising ethylene is carried out in one or more reactors preferably selected from continuous stirred-tank reactor, loop reactor, gas phase, or autoclave. According to certain embodiments, said process is carried out in one single reactor. According to other embodiments, said process is carried out in two or more reactors, connected in series. For instance, a process of the invention may be carried out in a double loop reactor.

Slurry polymerization is preferably used to prepare the ethylene polymers, preferably in at least one slurry loop reactor or at least one continuously stirred reactor. As used herein, the terms “loop reactor” and “slurry loop reactor” may be used interchangeably herein.

In certain preferred embodiments, the bridged metallocene catalyst is added to the reactor as catalyst slurry. As used herein, the term “catalyst slurry” refers to a composition comprising catalyst solid particles and a diluent. The solid particles can be suspended in the diluent, either spontaneously or by homogenization techniques, such as mixing. The solid particles can be non-homogeneously distributed in a diluent and form sediment or deposit.

As used herein, the term “diluent” refers to any organic diluent, which does not dissolve the synthesized polyolefin. As used herein, the term “diluent” refers to diluents in a liquid state, liquid at room temperature and preferably liquid under the pressure conditions in the reactor. Suitable diluents comprise but are not limited to hydrocarbon diluents such as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents, or halogenated versions of such solvents. Preferred solvents are C12 or lower, straight chain or branched chain, saturated hydrocarbons, C5-9 saturated alicyclic or aromatic hydrocarbons or C2-6 halogenated hydrocarbons. Non-limiting illustrative examples of solvents are n-butane, isobutane, n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, cycloheptane, methylcyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylenes, chloroform, chloroarenes such as chlorobenzene, tetrachloroethylene, dichloroethane and trichloroethane.

Alternatively, a suitable catalyst slurry diluent may also include a mineral oil, preferably, a mineral oil which is substantially free of impurities which may deleteriously interact with or kill the catalyst. Suitable mineral oils for use in the present context are well known to the skilled person.

In certain embodiments, the bridged metallocene catalyst can be pre-contacted with at least one alkenyl-aluminum compound of formula (I) before the catalyst is introduced into the reactor. Hence, in certain embodiments, a process is provided wherein said bridged metallocene catalyst is pre-contacted with alkenyl-aluminum compound of formula (I) before feeding to said at least one reactor. The alkylaluminum of formula AIR ^b _x can be introduced into the reactor separately.

Alternatively, the bridged metallocene catalyst can be pre-contacted with an alkylaluminum of formula AIR ^b _x before the catalyst is introduced into the reactor. Hence, in certain embodiments, a process is provided wherein said bridged metallocene catalyst is pre-contacted with said alkylaluminum of formula AIR ^b _x before feeding to said at least one reactor. The alkenyl-aluminum compound of formula (I) can be introduced into the reactor separately.

Alternatively, the bridged metallocene catalyst is pre-contacted before the catalyst is introduced into the reactor with at least one alkenyl-aluminum compound of formula (I) and an alkylaluminum of formula AIR ^b _x . In such embodiments, a mixture is prepared comprising said the bridged metallocene catalyst, said alkenyl-aluminum compound of formula (I) and said alkylaluminum of formula AIR ^b _x , and such mixture is fed to at least one reactor.

Still alternatively, the bridged metallocene catalyst can be introduced into the reactor without any pre-contact with the at least one alkenyl-aluminum compound of formula (I) and the alkylaluminum of formula AIR ^b _x . Both the compound of formula (I) and the alkylaluminum of formula Al R ^b _x can independently and separately be added to the reactor. A polymerization step in a process of the invention can be performed over a wide temperature range. In certain embodiments, the polymerization steps may be performed at a temperature from 20 °C to 125 °C, preferably from 60 °C to 110 °C, more preferably from 70 °C to 100 °C. Said temperature may fall under the more general term of polymerization conditions.

In certain embodiments, the polymerization steps may be performed at a pressure from about 20 bar to about 100 bar, preferably from about 30 bar to about 50 bar. Said pressure may fall under the more general term of polymerization conditions.

The invention also encompasses a catalyst system suitable for catalyzing a polymerisation process for preparing ethylene polymers having long chain branches, comprising a. at least one bridged metallocene catalyst which is not immobilized on an inert support, and preferably a bridged metallocene catalyst as defined herein, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I)

Wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and preferably wherein said alkenyl-aluminum compound of formula (I) is as defined herein.

The invention also encompasses a catalyst system suitable for catalyzing a polymerisation process for preparing ethylene polymers having long chain branches, comprising a. at least one bridged metallocene catalyst which is immobilized on an inert support, and preferably a bridged metallocene catalyst as defined herein, and b. at least one activating agent, wherein said activating agent comprises at least one alkenyl-aluminum compound of formula (I)

(R ¹ )n-AI-(R ² ) ₃ -n (I)

Wherein each R ¹ is selected from the group comprising alkyl, hydrogen, and halogen, wherein each R ² is -(CH2)m-CH2-CR ³ =CH2, wherein R ³ is an alkyl or hydrogen; wherein n is an integer or a non-integer from 0.1 to less than 3; and wherein m is an integer selected from 1 to 30, and preferably wherein said alkenyl-aluminum compound of formula (I) is as defined herein.

Said bridged metallocene catalyst is preferably supported on an inert support as defined herein, preferably a silica support.

In embodiments of a catalyst system of the invention, said alkenyl-aluminum compound of formula (I) compound is not provided on a support.

In embodiments of a catalyst system of the invention, said alkenyl-aluminum compound of formula (I) is provided as a solution in a diluent (solvent), as defined herein.

The invention also encompasses the use of a catalyst system as defined herein in a process for preparing ethylene polymers having long chain branches, preferably in a process as defined herein.

In certain embodiments, the invention encompasses the use of a catalyst system as defined herein in a process for preparing ethylene polymers having long chain branches in a homopolymerisation process as defined herein.

In certain embodiments, the invention encompasses the use of a catalyst system as defined herein in a process for preparing ethylene polymers having long chain branches in a copolymerisation process as defined herein.

The invention also encompasses an ethylene polymer having long chain branches (herein also “LCB”) obtained by a process as defined herein or obtained by a process using a catalyst system as provided herein.

LCB of ethylene polymers according to the present invention may be characterized in terms of their rheology long chain branching index (g _r heo). As used herein the long chain branching (LCB) index g _r he _O can be determined as described in the example section. A g _r heo of less than 1 indicates the presence of long chain branching, the value of g _r heo is decreasing with increasing long chain branching.

In some embodiments an ethylene polymer as provided herein has a rheology long chain branching index (g _r heo) lower than 0.90, preferably lower than 0.80, preferably lower than 0.75, preferably lower than 0.70, preferably lower than 0.65, preferably lower than 0.60, preferably lower than 0.55, as determined by the method disclosed in the example section. In some embodiments, an ethylene polymer as provided herein has a rheology long chain branching index (g _r heo) higher than 0.20, or higher than 0.25, or higher than 0.30, or higher than 0.35, or higher than 0.40, as determined by the method disclosed in the example section. In some embodiments, an ethylene polymer as provided herein has a rheology long chain branching index (g _r heo) comprised between more than 0.20 and less than 0.90. Preferably an ethylene polymer provided herein has a rheology long chain branching index g _r heo comprised between more than 0.25 and less than 0.80; such as from at least 0.30 to at most 0.70; or from at least 0.40 to at most 0.65, as determined by the method disclosed in the example section.

In some embodiments, an ethylene polymer as provided herein has a MI2, as determined according to ISO 1133:2005 Method B, condition D, at a temperature 190°C, and a 2.16 kg load using a die of 2.096 mm, up to 50 g/10 min, preferably comprised between 0.1 and 25 g/10 min, or between 0.1 and 20 g/10 min.

In some embodiments, an ethylene polymer as provided herein has a HLMI, as determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm, up to 150 g/10 min, such as between 1 and 100 g/10 min, or between 5 and 80 g/10 min.

In some embodiments, an ethylene polymer as provided herein has a ratio of weight average molecular weight (M _w ) to number average molecular weight (M _n ) [M _w /M _n ] of at least 2.0, preferably at least 2.2, preferably at least 2.3, preferably at least 2.4, preferably at least 2.5, preferably at least 2.6, preferably at least 2.7, preferably at least 2.8, preferably at least 2.9, preferably at least 3.0.

In some embodiments, an ethylene polymer as provided herein has a ratio of weight average molecular weight (M _w ) to number average molecular weight (M _n ) [M _w /M _n ] of] of at most 4.5 or at most 4.0, or at most 3.8, or to at most 3.5.

In some embodiments, an ethylene polymer provided herein has a ratio of weight average molecular weight (M _w ) to number average molecular weight (M _n ) [M _w /M _n ] of preferably from 2.0 to 4.5, such as from 2.5 to 4.5, such as from 2.7 to 4.0, such as from 2.8 to 4.0, such as from 2.9 to 3.5, such as from 3.0 to 3.5.

As used herein, the molecular weight (M _n (number average molecular weight), M _w (weight average molecular weight) and molecular weight distributions D (M _w /M _n ), and D' (Mz/Mw) were determined by size exclusion chromatography (SEC), such as gel permeation chromatography (GPC).

The present invention also relates to the use of an alkenyl-aluminum compound of formula (I) as defined herein as activating agent in a polymerization process, preferably a slurry polymerization process, for preparing ethylene polymers having long chain branches, preferably as defined herein, wherein said compound is used in combination with at least one bridged metallocene catalyst as defined herein, which is preferably immobilized on an inert support, preferably a silica support. In certain embodiments, an alkenyl-aluminum compound of formula (I) as defined herein is preferably used in a slurry polymerisation process for preparing ethylene polymers having long chain branches. An alkenyl-aluminum compound of formula (I) as defined herein is preferably used during such ethylene polymerization at a concentration of at most 3000 ppm, or at most 2000 ppm, or at most 1000 ppm, or at most 750 ppm, or at most 600 ppm, or at most 500 ppm, or most 400 ppm, or at most 350 ppm. An alkenyl- aluminum compound of formula (I) as defined herein is preferably used during such ethylene polymerization at a concentration of at least 10 ppm, such as at least 15 ppm, such as at least 20 ppm. Preferably, an alkenyl-aluminum compound of formula (I) as defined herein is preferably used during such ethylene polymerization at a concentration comprised between 10 and 3000 ppm, such as between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

Preferably, said alkenyl-aluminum compound of formula (I) as defined herein is used as a homogenous solution in a diluent, preferably a hydrocarbon diluent.

In certain embodiments, an alkenyl-aluminum compound of formula (I) as defined herein is used a homopolymerisation process as defined herein at a concentration of at most 3500 ppm, and preferably at a concentration comprised between 10 and 3000 ppm, or between 10 and 2000 ppm or between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

In certain other embodiments, an alkenyl-aluminum compound of formula (I) as defined herein is used in a copolymerisation process as defined herein at a concentration of at most 1000 ppm, and preferably at a concentration comprised between 10 and 1000 ppm, or between 10 and 750 ppm, or between 10 and 600 ppm, or between 10 and 500 ppm, or between 20 and 500 ppm.

The following examples serve to merely illustrate the invention and should not be construed as limiting its scope in any way. While the invention has been shown in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes and modifications without departing from the scope of the invention.

EXAMPLES

TEST METHODS

The properties cited herein and cited below were determined in accordance with the following test procedures. Where any of these properties is referenced in the appended claims, it is to be measured in accordance with the specified test procedure. Melt flow index

The melt flow index (MI2) of ethylene polymers was determined according to ISO 1133:2005 Method B, condition D, at a temperature 190 °C, and a 2.16 kg load using a die of 2.096 mm.

The melt flow index (HLMI) of ethylene polymers was determined according to ISO 1133:2005 Method B, condition G, at a temperature 190 °C, and a 21.6 kg load using a die of 2.096 mm.

Molecular weight, molecular distribution

The molecular weight (M _n (number average molecular weight), M _w (weight average molecular weight) and molecular weight distributions D (Mw/Mn), and D’ (Mz/Mw) were determined by size exclusion chromatography (SEC) and in particular by gel permeation chromatography (GPC). Briefly, a GPC-IR5 from Polymer Char was used: 10mg polyolefin sample was dissolved at 160 °C in 10 ml of trichlorobenzene for 1 hour. Injection volume: about 400pl, automatic sample preparation and injection temperature: 160 °C. Column temperature: 145 °C. Detector temperature: 160 °C. Two Shodex AT-806MS (Showa Denko) and one Styragel HT6E (Waters) columns were used with a flow rate of 1 ml/min. Detector: Infrared detector (2800-3000 cm ^-1 ). Calibration: narrow standards of polystyrene (PS) (commercially available). Calculation of molecular weight Mi of each fraction i of eluted polyolefin is based on the Mark-Houwink relation (logio(MpE) = 0.965909 x logio(Mps) - 0.28264) (cut off on the low molecular weight end at MPE = 1000).

The molecular weight averages used in establishing molecular weight/property relationships are the number average (M _n ), weight average (M _w ) and z average (M _z ) molecular weight. These averages are defined by the following expressions and are determined form the calculated Mi: d NiMt Xd ™i Xi hi M ⁿ ~ i Nt ~ _i W _i /M _i ~ X _li h _i /M _i

Here Nj and Wj are the number and weight, respectively, of molecules having molecular weight Mi. The third representation in each case (farthest right) defines how one obtains these averages from SEC chromatograms, hi is the height (from baseline) of the SEC curve at the i _t h elution fraction and Mj is the molecular weight of species eluting at this increment.

Differential Scanning Calorimetry (DSC) for Determination of Crystallization and Melting Temperatures.

Peak crystallization temperature (T _c ), peak melting temperature (T _m ) and heat of fusion (A%) were measured via Differential Scanning using DQ 2000 instrument by TA Instruments, calibrated with indium and using T zero mode. The polymer analysis was performed with a 2 to 10 mg of polymer sample. The sample was first equilibrated at 40 °C and subsequently heated to 220 °C using a heating rate of 50 °C/min (first heat). The sample was held at 220 °C for 3 min to erase any prior thermal and crystallization history. The sample was subsequently cooled down to 30 °C with a constant cooling rate of 10 °C/min (first cool). The sample was held isothermal at 30 °C for 2 min before being heated to 220 °C at a constant heating rate of 10 °C/min (second heat). The exothermic peak of crystallization (first cool) was analyzed using the TA Universal Analysis software and the peak crystallization temperature (T _c ) corresponding to 10 °C/min cooling rate was determined. The endothermic peak of melting (second heat) was also analysed using the TA Universal Analysis software and the peak melting temperature (T _m ) corresponding to 10 °C/min heating rate was determined. Unless otherwise indicated, reported values of T _c , T _m in this invention refer to a cooling and heating rate of 10 °C/min, respectively.

Long chain branching index g _r heo

Rheology long chain branching index g _r heo was measured according to the formula, as described in WO 2008/113680: wherein Mw (SEC) is the weight average molecular weight obtained from size exclusion chromatography expressed in kDa; and wherein Mw (r| ₀ , MWD, SCB) is determined according to the following, also expressed in kDa: = exp(l .7789 + 0.199769 LnM _n + 0.209026(Ln rj ₀ ) + 0.955(ln p)

- 0.007561( / )(£n/; ₀ ) + 0.02355(lnM , ) ² ) wherein the zero shear viscosity qO in Pa.s is obtained from a frequency sweep experiment combined with a creep experiment, in order to extend the frequency range to values down to 10' ⁴ s' ¹ or lower, and taking the usual assumption of equivalence of angular frequency (rad/s) and shear rate; wherein zero shear viscosity qO is estimated by fitting with Carreau- Yasuda flow curve (q-W) at a temperature of 190°C, obtained by oscillatory shear rheology on ARES-G2 equipment (manufactured by TA Instruments) in the linear viscoelasticity domain; wherein circular frequency (W in rad/s) varies from 0.05-0.1 rad/s to 250-500 rad/s, typically 0.1 to 250 rad/s, and the shear strain is typically 10 %. In practice, the creep experiment is carried out at a temperature of 190 °C under nitrogen atmosphere with a stress level such that after 1000 s the total strain is less than 25 %; wherein the apparatus used is either an AR-G2 or an ARES-G2 manufactured by TA instruments.

Small amplitude oscillatory shear (SAPS)

Dynamic shear viscosity (or complex viscosity) as a function of frequency is determined by small-amplitude oscillatory shear (SAGS) rheology. Complex viscosity is measured at 190 °C over an angular frequency range from 0.1 to 200 rad/s or from 0.1 to 250 rad/s using the procedure described below using Small Amplitude Oscillatory Shear (SAGS) testing.

From the data generated by such a test, it is possible to determine the phase or loss angle 5, which is the inverse tangent of the ratio of G" (the loss modulus) to G' (the storage modulus). For a typical linear polymer, the loss angle at low frequencies (or long times) approaches 90° making the loss modulus much larger than the storage modulus. As frequencies increase, more of the chains relax too slowly to absorb energy during the oscillations, and the storage modulus grows relative to the loss modulus. Eventually, the storage and loss moduli become equal and the loss angle reaches 45°. In contrast, a branched chain polymer relaxes very slowly. Such branched polymers never reach a state where all its chains can relax during an oscillation, and the loss angle never reaches 90° even at the lowest frequency, co, of the experiments. The loss angle is also relatively independent of the frequency of the oscillations in the SAGS experiment; another indication that the chains cannot relax on these timescales.

In a plot of the phase angle 5 versus the measurement frequency co, polymers that have long chain branches exhibit a plateau in the function of b(co), whereas linear polymers do not have such a plateau. According to Garcia-Franco et al. (34(10) Macromolecules 3115- 3117 (2001)), the plateau in the aforementioned plot will shift to lower phase angles 5 when the amount of long chain branching occurring in the polymer sample increases. van Gurp-Palmen plot (vGP plot)

Complex modulus, G*, and loss angles, 5, may be obtained from rheological data determined at the test temperature of 190°C and analyzed using the van Gurp-Palmen treatment (reference: van Gurp, M. and Palmen, J., Rheology Bulletin, 1998, 67(1), 5-8). The vGP curve is a plot of phase angle 5 (= tan ^-1 [G'7G']) versus magnitude of the complex modulus, |G*|. In linear polymers, for a decrease of the modulus value, 5 will initially drop, it will then pass a minimum, rises again, moves through an inflection point, and finally approaches its limiting value of 90°. LCB shifts the vGP curve down. The higher the LCB density, the lower the 5 values. The area included under the vGP curve can be used as a parameter to evaluate the degree of LCB. In addition, the magnitude of the drop at the apparent plateau caused by LCB is related to the relative length of long chain branches on the polymer backbone. Low levels of long chain branching can be detected and quantified on a relative basis, using this methodology.

LCB concentration

Long Chain Branching may be determined according to the methods known in the art such as for instance reported in Liu et al. 2017 (Macromol. React. Eng., 11 , page 1600012: A comprehensive review of controlled synthesis of long chain branched polyolefins: part 3: Characterization of Long Chain Branched polymers), which is incorporated by reference herein in its entirety. For example, long chain branches may be determined by methods based on ¹³ C NMR spectroscopy, or by SEC-VISCO according to the method as disclosed in W02009/059971. Long chain branching may also be determined by rheology using any one of the methods disclosed in W02009/059971.

MATERIALS and METHOD INFORMATION applicable to the below examples 1 to 4

All manipulations were performed under a purified argon atmosphere using standard Schlenk or glovebox techniques. Dry toluene was obtained from a MB-SPS-800 solvent purification system and stored over molecular sieves 3 . Deuterated benzene was dried over calcium hydride and distilled under reduced pressure prior to use. rac-{EBTHI}ZrCl2, rac-{EBTHI}ZrCl2-supported onto silica (from PQ, D50: 40 p) (0.4 wt% Zr) and MAO (30 wt% solution in toluene; contains ca. 10 wt% of free AIMes). Other starting materials were purchased from Fluorochem and Acros and used as received.

Supported catalyst: rac-{EBTHI}ZrCl2-supported onto silica was prepared as follows. rac-ethylene-bis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride (CAS Number 100163-29-9) was supported on silica which has been previously activated with methylalumoxane (MAO) as follows: MAO treatment: Methylaluminoxane (30 wt%) (MAO) in toluene (obtained from Albemarle) was used as the activator. Silica (from PQ corporation) was used as catalyst support and it was dried at 450 °C under nitrogen for 6 h. 10 g of the dried silica was introduced in a 500 mL round-bottomed flask. Toluene was added and the suspension was stirred at 100 rpm. MAO (30 % by weight in toluene) was dropwise added via a dropping funnel and the resulting suspension was heated at 110 °C (reflux) for 4 hours. The amount of added MAO was calculated in order to reach the desired Al loading. After the reflux, the suspension was cooled down to room temperature and the mixture was filtered through a glass frit. The recovered powder was washed with toluene and pentane before being dried under reduced pressure overnight.

Metallocene treatment: In a 250 mL round bottom flask, 9.8 g of the above-obtained MAO- support was suspended in 80 mL of toluene. Then, 0.2g of rac-ethylene-bis(4,5,6,7- tetrahydro-1-indenyl)]zirconium dichloride (formula X) (CAS Number 100163-29-9) was dissolved in 20 mL of toluene and slowly added to the suspended silica-containing support . The resulting suspension was stirred at 100 rpm for 2 hours at room temperature. Solvent was removed by filtration. The obtained catalyst was washed with /so-hexane, filtered and dried at room temperature.

NMR spectra of Al-alkenyl species were recorded on a Bruker AC-400 spectrometer in Teflon-valved NMR tubes at 25 °C. ¹ H and ¹³ C NMR chemical shifts are reported in ppm vs. SiMe4 (0.00) as determined by reference to the residual solvent peak. ¹³ C{ ¹ H} NMR analyses of PE samples were conducted on a AM-500 Bruker spectrometer equipped with a cryoprobe using the following conditions: solutions of ca. 200 mg of polymer in a mixture 5: 1 of 1 ,2,4-trichlorobenzene/CeD6 mixture at 135 °C in 10 mm tubes, inverse-gated experiment, pulse angle = 90 °, delay = 11 s, acquisition time = 1 .25 s, number of scans = 6,000.

DSC measurements were performed on a SETARAM Instrumentation DSC 131 differential scan calorimeter at a heating rate of 10 °C. min ^-1 ; first and second runs were recorded after cooling to 30 °C; the melting and crystallization temperatures reported in tables were determined on the second run.

SEC analyses of PE samples were carried out in 1 ,2,4-trichlorobenzene at 135 °C using polystyrene standards for universal calibration.

Rheological measurements: samples for rheological measurements in this example section were prepared as follows: ca. 900 mg of polymer were stabilized with 1 wt% of BHT or IRGANOX 1010 and press-moulded into circular disks (2 mm thick and 20 mm diameter) at 190 °C. Oscillatory experiments were carried out on an ARES G2 equipment (TA Instruments) in parallel plate configuration under the following conditions: shear strain (Y) 10%, angular frequencies (co) from 0.1 to 250 rad.s ¹ , T = 190 °C, N2 atmosphere.

General polymerization procedure: Polymerization experiments were performed in a 300 mL-high-pressure glass reactor equipped with a mechanical stirred (Pelton turbine) and externally heated with a double mantle with thermostated circulating water bath. The reactor was purged three times (vacuum-argon cycles) and charged with toluene (150 mL). MAO (1.5 mL of a 30wt% solution in toluene), and ethylene were introduced. The system was thermally equilibrated at the desired temperature for 30 min. Ethylene pressure was decreased to 1 bar and a mixture of catalyst and co-reactants (co-activators such as Tibal and/or alkenyl aluminum agent) in toluene (circa 2 mL) was added by syringe (injected). The ethylene pressure was increased to 4 barg (kept constant by means of a back regulator) and the reaction mixture was stirred for the desired time. The temperature inside the reactor was monitored using a thermocouple. The polymerization was stopped by venting the reactor and quenching with a 10 wt% solution of aqueous HCI in methanol (ca. 3 mL). The polymer was precipitated from methanol (200 mL) and 35 wt% aqueous HCI (2 mL) was added to dissolve possible catalyst residues. The polymer was collected by filtration, washed with methanol (200 mL) and dried under reduced pressure at 65 °C overnight.

Optimized Synthesis of Al-alkenyl activating agent: Under an Ar atmosphere, a Schlenk flask equipped with a magnetic stir bar was charged with 1 ,7-octadiene (20 mL, 14.9 g, 135 mmol, 10 equiv.) and DIBAL-H (11.7 mL of a 1.2 M solution in toluene, 13.5 mmol, 1 equiv.) was added dropwise. The mixture was stirred at 110 °C for 1 h and then at 70 °C for 16 h (Procedure A) or at 85 °C for 16 h (Procedure B). Volatiles were removed under reduced pressure affording a colourless oil. The composition of the reaction mixture was determined by ¹ H NMR spectroscopy. For the sample prepared according to Procedure A it was found to be 'Buo.89AI(1-oct-7-en-yl)2.n. However, the sample contained 7-methylenepentadeca-1 ,14-diene as side-product (see Figure 1). On the other hand, no side-product was found in the batch prepared according to Procedure B, and the composition was found to be 'Bui.09AI(1-oct-7-en-yl)i.9i. The latter compound was used in examples 2 and 3 reported below (and was also named AI-1 in these examples) (see FIGURE 2).

Yield 3.76 g, 96%. ¹ H NMR (400 MHz, C ₆ D ₆ , 298 K): 5 = 5.86-5.73 (m,=CH-octenyl), 5.07- 4.99 (m, =C/-/2-octenyl), 2.12-1.92 (m, -CH=C/72-octenyl overlapped with C/7-'Bu), 1.58- 1.37 (m, C/73-'BU overlapped with C/72-octenyl), 1.06 (d, ³ JH-H = 6.2 Hz, CHs-'Bu), 0.52-0- 48 (m, AI-C/72-octenyl) 0.30 (d, ³ J _H -H = 6.9 Hz, AI-CH ₂ -'Bu). Computational details: All calculations were carried out with the Gaussian 09 suite of programs (see Gaussian 09, Revision D.01 , Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, M. J.; Kiene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann,

R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich,

S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2009). Zirconium atoms were treated with the very small core Stuttgart-Dresden effective core potential associated with its adapted basis sets and additional f and g polarization functions (see (a) Andrae, D.; Haeussermann, II.; Dolg, M.; Stoll, H.; Preuss, H. Theor. Chim. Acta 1990, 77, 123-141. (b) Martin, J. M. L.; Sundermann, A. J. Chem. Phys. 2001 , 114, 3408-3420). Carbon and hydrogen atoms were described with a 6-31G(d,p) double-^ basis set (Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257-2261). Silicon atoms have been treated with the small core Stuttgart-Dresden effective core potential associated with its adapted basis set and additional d polarization functions (Bergner, A.; Dolg, M.; Kuechle, W.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, 1431). Calculations were carried out at the DFT level of theory with the hybrid functional B3PW91 (see (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648- 5652. (b) Burke, K.; Perdew, J. P.; Yang, W. in Electronic Density Functional Theory: Recent Progress and New Directions, Eds: Dobson, J. F.; Vignale, G.; Das, M. P., Plenum, New York, 1998). Solvation energies were evaluated by a self-consistent reaction field (SCRF) approach based on accurate numerical solutions of the Poisson-Boltzmann equation by using the SMD solvation model (Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378-6396). Toluene was used as solvent. All geometries were optimized without any symmetry restriction and the nature of the extrema was verified by analytical frequency calculations. The calculation of electronic energies and enthalpies of the extrema of the potential energy surface (minima and transition states) were performed at the same level of theory as the geometry optimizations. Enthalpies were obtained at T = 298 K within the harmonic approximation.

Cartesian coordinates are shown below. Cartesian Coordinates

! Active Catalyst ! H -2.839452 3.382738 0.311790 scf done: -863.282385 H -3.617964 1.989115 1.084354

C 0.061784 2.618286 -1.906739 H -1.882522 1.973059 0.794112

C -1.261571 2.455165 -2.605863

C -2.239724 3.493958 -2.631371 ! Ethylene Monomer !

C -2.027849 4.844256 -2.005402 scf done: -78.561376

C -0.750439 4.898193 -1.152801 C 0.138668 -0.266277 0.093858

C 0.400101 4.111544 -1.783522 C 0.146459 -0.030817 1.403036

C -3.289597 3.073676 -3.492640 H 1.024180 -0.116972 -0.519947

C -2.955666 1.796495 -4.016907 H -0.753581 -0.616591 -0.420920

C -1.705933 1.393743 -3.460541 H 1.038964 0.321087 1.916159

Zr -3.394124 1.364022 -1.644734 H -0.739091 -0.179595 2.016819

C -2.831362 -0.961176 -2.356043 C -4.252355 -0.961213 -2.228062 ! Co-Catalyst ! C -4.579567 -0.772966 -0.844742 scf done: -787.383539 C -3.365879 -0.650742 -0.124829 C 1.553379 2.500668 -0.654374 C -2.294131 -0.752814 -1.050294 Al 2.459252 1.336368 0.693350 C -5.996025 -0.784544 -0.330098 C 1.822557 -0.530919 1.000676 C -6.934596 -1.440981 -1.350799 C 0.313505 -0.818090 0.916509 C -6.706415 -0.895103 -2.762291 C -0.457553 -0.041728 1.986675 C -5.298979 -1.228915 -3.276563 C 4.151922 1.824739 1.629842 C -2.016160 -1.085566 -3.617004 C 4.884953 3.117255 1.250131 C -1.017932 0.079977 -3.733281 C 6.220859 3.310331 1.975407

C -2.840258 2.285966 0.362582 C 6.939160 4.608268 1.602939

H 0.843519 2.095446 -2.468252 C 8.279698 4.792391 2.315127

H -0.460603 5.944797 -1.013080 C 8.986496 6.103405 1.940603

H -1.949952 5.571292 -2.825772 C 10.283001 6.301490 2.668035

H 1.308914 4.231060 -1.184778 C 11.478606 6.434921 2.092871

H -0.950172 4.494887 -0.153055 C 0.013388 -2.316991 1.023082

H -2.898197 5.157153 -1.415582 H 0.528675 -2.882022 0.237899

H -3.268561 -0.520519 0.945201 H 0.348640 -2.715199 1.989282

H -6.349245 0.236181 -0.114023 H -1.060087 -2.525160 0.932737

H -6.761939 -2.524906 -1.353883 H -0.123859 -0.324610 2.993320 H -7.449650 -1.305185 -3.453332 H -0.314519 1.041939 1.884201 H -5.088157 -0.693012 -4.209825 H -1.535865 -0.232205 1.932075 H -5.254839 -2.296960 -3.531618 H 12.383538 6.571388 2.679950 H -6.863504 0.194806 -2.761110 H 11.597679 6.416071 1.010677

H -7.974558 -1.287672 -1.045725 H 10.217542 6.325208 3.757898 H -6.032170 -1.314291 0.628068 H 9.161611 6.134386 0.857589

H -4.166398 3.658336 -3.754404 H 8.311558 6.941263 2.172320

H -1.239971 -0.718726 -0.799205 H 8.122228 4.762814 3.402505 H 0.622681 4.514557 -2.780427 H 8.941914 3.948309 2.080238

H 0.043080 2.168234 -0.905881 H 7.100733 4.634806 0.515560

H -3.542370 1.228411 -4.729946 H 6.286652 5.463382 1.832162

H -2.683905 -1.094439 -4.484224 H 6.046826 3.286945 3.061011 H -1.482393 -2.043386 -3.631419 H 6.875634 2.454313 1.756596 H -0.557634 0.085357 -4.728704 H 5.068201 3.142196 0.166147

H -0.201766 -0.056410 -3.016972 H 4.243251 3.984011 1.460658 H 3.947776 1.819598 2.713543 C 0.180814 0.952276 -2.063217

H 4.826772 0.963379 1.485956 C 1.499062 3.608023 0.261288

H 2.351910 -1.157035 0.260938 C 2.786798 3.406333 1.072910

H 2.207098 -0.875372 1.974281 C 3.841012 2.617796 0.293019

H -0.050014 -0.479575 -0.065632 C 3.351977 1.200586 -0.040132

H 0.525408 2.136248 -0.797608 H 4.060917 0.699780 -0.708602

C 1.531973 4.016639 -0.410534 H 3.184474 4.384693 1.362278

H 2.054655 2.294183 -1.615351 H 1.648742 4.420381 -0.463532

H 1.038714 4.527915 -1.251370 H 4.769062 2.555932 0.870938

C 0.817611 4.414102 0.882243 H 2.558141 2.873327 2.003197

H 2.557744 4.407808 -0.385366 H 0.682112 3.939207 0.913678

C 0.747545 5.924020 1.113134 H 0.290335 -1.792107 2.689726

H -0.201950 4.002047 0.871661 H -3.094700 -1.371258 1.935713

H 1.326715 3.941152 1.738354 H -2.902436 -4.231246 0.863651

C 0.022855 6.313996 2.401840 H -4.160332 -3.399704 -1.130290

H 1.766069 6.337499 1.129138 H -2.296251 -1.872641 -2.131437

H 0.242883 6.395288 0.257523 H -1.887496 -3.516770 -1.711311

C -0.057488 7.832773 2.613425 H -4.068274 -1.764421 -0.527069

H -0.993621 5.895907 2.389123 H -4.365585 -3.375575 1.334753

H 0.528638 5.858903 3.263957 H -2.349118 -2.740752 2.733865

C -0.805348 8.213082 3.856693 H -0.824789 2.869409 -1.494480

H 0.953742 8.258101 2.645703 H 2.088666 -1.765818 0.689847

H -0.557488 8.280378 1.741056 H 4.083881 3.145494 -0.638778

C -0.303219 8.907871 4.878059 H 3.323862 0.605867 0.882569

H -1.842218 7.874350 3.909797 H -0.487767 0.541723 -2.812265

H -0.900272 9.147089 5.754718 H 0.189697 -1.946015 -2.789431

H 0.724716 9.266966 4.874643 H 1.442111 -3.026840 -2.203877

H 2.322504 -0.826453 -3.187014

! First Insertion of Ethylene to Catalyst - H 2.885565 -1.167451 -1.561433

Adduct ! H 0.241807 2.162768 2.368559 scf done: -941.852101 H -0.371208 0.660883 3.092026

C -1.065971 -2.131892 -0.355864 H 1.324722 0.796892 2.655357

C 0.320512 -2.033967 -0.660151 H -2.639225 1.311198 2.161654

Zr -0.200074 0.233137 0.265493 H -2.070852 2.639675 1.006642

C -3.043509 0.980490 0.102828 H -3.008419 1.371058 -0.912711

C -2.532827 1.663761 1.139076 H -3.580143 0.049631 0.255501

C 0.310542 1.068095 2.332343

C -2.182445 -2.552111 -1.277439 ! First Insertion of Ethylene to Catalyst -

C -3.529247 -2.719122 -0.549523 Transition State !

C -3.377852 -3.242014 0.881229 scf done: -941.479861

C -2.533542 -2.297415 1.749695 C -4.263499 -0.935409 -2.199480

C -1.220184 -2.030812 1.063989 C -2.879312 -0.836977 -2.534651

C 1.014368 -1.853535 0.574843 Zr -3.375276 1.427478 -1.628953

C 0.065743 -1.864449 1.633524 C -5.681598 2.084232 -1.755177

C 0.962005 -2.057376 -2.021103 C -5.429023 2.726750 -0.537360

C 1.992445 -0.923500 -2.145840 C -3.443040 2.504316 0.421436

C 1.418274 0.379138 -1.652892 C -5.405128 -1.341197 -3.097101

C 1.994902 1.264462 -0.689482 C -6.736573 -1.490482 -2.337349

C 1.122015 2.379314 -0.517726 C -6.558609 -2.036169 -0.918969

C -0.003072 2.175384 -1.357150 C -5.686163 -1.103797 -0.066019 C -4.387623 -0.844947 -0.778257 C 0.413336 -2.164155 -0.691771

C -2.159010 -0.657498 -1.315528 Zr -0.080722 0.090070 0.228454

C -3.090642 -0.674593 -0.240174 C -2.145458 0.926825 0.662958

C -2.273500 -0.864742 -3.914252 C -1.747329 1.934364 1.765103

C -1.243672 0.265125 -4.081792 C -0.655081 1.428180 2.726528

C -1.796871 1.574466 -3.582031 C -2.120551 -2.525083 -1.356128

C -1.218477 2.436829 -2.602740 C -3.482100 -2.403828 -0.659418

C -2.095564 3.552024 -2.409836 C -3.479295 -3.096195 0.705803

C -3.210489 3.373831 -3.265901 C -2.491138 -2.434314 1.677126

C -3.036547 2.158796 -3.981187 C -1.169817 -2.189985 1.005112

C -1.721309 4.754319 -1.587520 C 1.088068 -2.048251 0.557324

C -0.478152 4.491469 -0.727207 C 0.112918 -2.041343 1.593007

C 0.605343 3.748029 -1.511791 C 1.074604 -2.186262 -2.045146

C 0.135286 2.350999 -1.942471 C 2.074109 -1.025548 -2.176986

H 0.855851 1.905010 -2.636854 C 1.442543 0.267125 -1.729177

H -0.088879 5.444391 -0.354282 C 1.965790 1.224751 -0.813703

H -1.509455 5.578676 -2.282363 C 1.015483 2.286982 -0.673571

H 1.515455 3.656148 -0.910040 C -0.109982 1.969812 -1.476014

H -0.752396 3.901084 0.157965 C 0.149469 0.731505 -2.122717

H -2.559610 5.096045 -0.968498 C 1.323422 3.560814 0.064889

H -2.844807 -0.602013 0.813118 C 2.575419 3.427311 0.940894

H -6.236680 -0.171827 0.125591 C 3.704574 2.702190 0.205531

H -6.094084 -3.030088 -0.957497 C 3.317890 1.258588 -0.144356

H -7.398447 -2.146311 -2.912354 H 4.069163 0.808755 -0.802321

H -5.530685 -0.652091 -3.941007 H 2.904859 4.423368 1.253362

H -5.135830 -2.308164 -3.542922 H 1.498012 4.338913 -0.691293

H -7.251186 -0.523102 -2.281326 H 4.615284 2.699537 0.812907

H -7.536486 -2.163190 -0.442821 H 2.334022 2.881297 1.864589

H -5.485865 -1.548303 0.914690 H 0.466017 3.907637 0.651568

H -4.033170 4.069233 -3.383182 H 0.322070 -2.003187 2.657120

H -1.081872 -0.583353 -1.221056 H -2.922751 -1.498060 2.054833

H 0.873274 4.330448 -2.403120 H -3.208965 -4.152377 0.574909

H 0.116278 1.691701 -1.063283 H -4.254467 -2.839354 -1.301736

H -3.712729 1.761446 -4.729875 H -2.081283 -1.876832 -2.239297

H -3.068282 -0.753649 -4.659446 H -1.994134 -3.550141 -1.732894

H -1.803067 -1.836760 -4.108471 H -3.739165 -1.344593 -0.531257

H -0.951532 0.352234 -5.135187 H -4.483419 -3.080895 1.141963

H -0.330400 0.023590 -3.528678 H -2.335112 -3.069619 2.556550

H -3.356803 3.573064 0.617647 H -0.990479 2.584077 -1.613048

H -3.774480 1.986183 1.322079 H 2.162133 -1.993067 0.696296

H -2.385401 2.155093 0.233136 H 3.941785 3.245450 -0.718433

H -5.817680 2.308593 0.385256 H 3.327675 0.655052 0.776045

H -5.275109 3.800511 -0.522606 H -0.509061 0.241296 -2.831274

H -5.753687 2.683116 -2.657501 H 0.307043 -2.108265 -2.821902

H -6.269061 1.173329 -1.742064 H 1.582078 -3.144556 -2.209355

H 2.421589 -0.941054 -3.213976

! First Insertion of Ethylene to Catalyst - H 2.962488 -1.228041 -1.569652 Product ! H -0.459877 2.160416 3.516867 scf done: -941.878403 H -0.932593 0.490126 3.217762

C -0.988221 -2.243718 -0.407003 H 0.359963 1.307212 2.281582 H -2.619787 2.183944 2.383775 H -0.179494 3.458952 1.560587

H -1.416276 2.880819 1.323259 H -2.015944 3.808077 -0.177201

H -2.688899 1.429621 -0.142553 H -4.913932 -2.532524 1.821689

H -2.819333 0.173469 1.083336 H -3.606656 0.159798 -3.200481

H -7.508460 -3.284193 -2.386612

! Second Insertion of Ethylene to H -5.891186 -0.783328 -3.073070 Catalyst - Adduct ! H -2.599352 -2.945068 0.491785 scf done: -1020.445395 H -0.906122 -2.098268 -1.378014

C -5.948381 -1.827585 -2.738271 H -0.897004 -1.592399 -3.056329

C -5.149100 -2.040921 -1.478014 H -2.441731 -3.588408 -2.545765

C -5.758769 -2.057729 -0.187724 H -3.210594 -2.256486 -3.386276

C -7.241171 -1.948408 0.021751 H -4.536023 0.047543 3.712221

C -7.974052 -1.504477 -1.251347 H -3.085962 1.182811 3.531026

C -7.419867 -2.195487 -2.498322 H -3.052420 -1.907915 3.376749

C -4.757958 -2.400065 0.757222 H -1.599787 -0.778688 3.194020

C -3.539886 -2.630613 0.052374 H -6.600420 2.990743 0.712931

C -3.774940 -2.416162 -1.334904 H -5.062508 3.147403 -0.105028

Zr -3.906804 -0.198957 -0.164502 H -6.666505 0.546090 0.191513

C -5.717389 1.089930 0.173954 H -5.328501 0.991501 1.231930

C -5.993688 2.567199 -0.101987

C -6.742515 2.791954 -1.413168 ! Second INsertion of Ethylene to

C -2.752165 -2.542876 -2.434676 Catalyst - Transition State !

C -1.528424 -1.652461 -2.160888 scf done: -1019.888523

C -1.968862 -0.278359 -1.734209 C -2.019884 -2.880764 -1.693734

C -1.468357 0.502600 -0.654399 C -1.234499 -2.185715 -0.609409

C -2.218042 1.721717 -0.595186 C -1.814769 -1.773479 0.630053

C -3.171589 1.698600 -1.642920 C -3.278773 -1.953122 0.919563

C -3.032921 0.464659 -2.333107 C -3.811402 -3.148443 0.115940

C -1.857089 2.852916 0.334834 C -3.525290 -2.979508 -1.377193

C -0.396023 2.717866 0.784421 C 0.183732 -2.080918 -0.501841

C -0.099773 1.308755 1.301191 C 0.471568 -1.579564 0.802756

C -0.255971 0.249236 0.201240 C -0.760721 -1.395176 1.493458

C -3.473591 0.166600 3.510726 Zr -0.484970 0.321857 -0.394717

C -2.673030 -0.890159 3.330307 C 1.633892 0.036974 -1.724878

H -6.913427 3.858432 -1.594191 C 1.927648 1.119229 -0.840777

H -7.722961 2.302763 -1.394645 C 1.115300 2.237338 -1.212759

H -6.191236 2.389957 -2.271321 C 0.299001 1.834465 -2.293893

H -5.532921 -2.434444 -3.550055 C 0.612685 0.482985 -2.613616

H -9.042795 -1.716218 -1.142560 C 1.321554 3.614790 -0.648520

H -7.600474 -2.944155 0.317154 C 2.213909 3.594486 0.598709

H -8.011535 -1.918957 -3.377238 C 3.427917 2.683251 0.404833

H -7.880964 -0.418715 -1.377826 C 3.011847 1.219167 0.204064

H -7.481542 -1.286624 0.863227 C 2.258189 -1.333373 -1.699663

H -3.857951 2.494135 -1.897448 C 1.191148 -2.430896 -1.564851

H -2.508169 2.877029 1.219594 C -2.610708 0.641849 -1.608439

H 0.265885 2.942244 -0.062244 C -2.887241 1.494219 -0.552095

H 0.915345 1.256401 1.707683 C -1.224038 1.966603 1.049570

H -0.259313 -0.760664 0.630043 C -2.155578 2.347016 2.190069

H 0.622224 0.283313 -0.458393 C -2.631949 1.213685 3.089061

H -0.778383 1.086181 2.136059 H 3.875796 0.619546 -0.103422 H 2.538193 4.614947 0.827316 C 1.427993 1.803683 -1.254091

H 1.808449 4.216673 -1.428372 C 0.612307 1.130968 -2.198525

H 4.100516 2.755868 1.265719 C 1.042044 -0.221517 -2.270072

H 1.637469 3.250831 1.468869 C 1.454053 3.263206 -0.895610

H 0.370138 4.121486 -0.442770 C 2.323925 3.522089 0.340605

H -0.867531 -1.069666 2.520474 C 3.649721 2.761759 0.263585

H -3.858170 -1.059285 0.649706 C 3.439277 1.240995 0.251814

H -3.343544 -4.070603 0.484303 C 2.891375 -1.682123 -1.127673

H -3.948040 -3.817881 -1.940539 C 1.906979 -2.854236 -0.980479

H -1.872185 -2.413505 -2.675138 C -1.947560 0.924287 -0.424143

H -1.609209 -3.894926 -1.787194 C -2.472628 1.433236 0.937136

H -4.052994 -2.086110 -1.734995 C -1.430841 2.247579 1.718248

H -4.889226 -3.251635 0.279758 C -1.916131 2.839061 3.045305

H -3.429397 -2.107066 1.993079 C -2.279095 1.813810 4.115463

H -0.408134 2.463993 -2.821215 H 4.377690 0.727019 0.016917

H 1.459646 -1.437379 1.225081 H 2.508534 4.596672 0.437135

H 3.998329 3.020502 -0.470638 H 1.872882 3.810578 -1.751457

H 2.684010 0.804085 1.166987 H 4.294520 3.034145 1.105208

H 0.176805 -0.092935 -3.422144 H 1.783793 3.222286 1.251416

H 0.670397 -2.562856 -2.518924 H 0.441053 3.658884 -0.757339

H 1.666668 -3.394015 -1.339767 H -0.778373 -1.489147 2.728027

H 2.850351 -1.497945 -2.607856 H -3.378460 -1.229263 0.553445

H 2.959241 -1.390633 -0.861049 H -3.155441 -4.212145 -0.071526

H -2.821135 2.569996 -0.681210 H -3.213934 -3.508936 -2.498959

H -3.500928 1.159541 0.278128 H -0.799328 -2.674244 -2.607123

H -2.332460 1.053258 -2.573181 H -1.038779 -4.159817 -1.713131

H -3.046019 -0.350081 -1.614224 H -3.005247 -1.835796 -1.999934

H -0.327204 1.428410 1.491698 H -4.497491 -3.130511 -0.427071

H -1.651664 3.101598 2.810979 H -3.224360 -2.539815 1.710226

H -3.021066 2.871630 1.762833 H -0.185754 1.572548 -2.781071

H -3.336108 1.589301 3.838342 H 1.730048 -1.925077 1.838915

H -3.138976 0.425593 2.523913 H 4.181163 3.056907 -0.650367

H -1.797585 0.755638 3.631474 H 3.166492 0.908106 1.266396

H -0.841779 2.880071 0.586718 H 0.641567 -0.976901 -2.935723

H 1.519275 -3.138736 -1.963687

! Second Insertion of Ethylene to H 2.428242 -3.735710 -0.589789 Catalyst - Product ! H 3.603234 -1.886448 -1.937151 scf done: -1020.486133 H 3.485981 -1.580040 -0.213887

C -1.256809 -3.082371 -1.698855 H -3.361047 2.066280 0.792458

C -0.635256 -2.512908 -0.452725 H -2.808478 0.592231 1.556663

C -1.410879 -2.102855 0.674353 H -1.832178 1.778223 -1.103087

C -2.910403 -2.207871 0.714291 H -2.682218 0.256961 -0.893871

C -3.405863 -3.183180 -0.362358 H -0.544259 1.606182 1.940353

C -2.776495 -2.873513 -1.722077 H -1.143903 3.512434 3.437174

C 0.748449 -2.491687 -0.088254 H -2.788887 3.470233 2.831089

C 0.820637 -2.037443 1.257013 H -2.592525 2.311497 5.038591

C -0.505511 -1.790497 1.722273 H -3.103434 1.163793 3.803967

Zr 0.100971 -0.074041 -0.030454 H -1.422399 1.175826 4.367849

C 2.154769 -0.393433 -1.383719 H -1.063297 3.061495 1.079499

C 2.379859 0.859678 -0.752522 ! Third Insertion of Ethylene to Catalyst H 0.541034 0.060224 -3.337340 - Adduct ! H 1.284240 -2.535431 -2.781738 scf done: -1099.049823 H 2.539356 -3.390796 -1.905823

C -1.155080 -3.532880 -1.482489 H 3.311617 -1.209528 -3.005152

C -0.292862 -2.750776 -0.527979 H 3.671534 -1.330098 -1.293456

C -0.696537 -2.485748 0.820767 H -1.437410 2.924181 0.805540

C -2.048806 -2.863005 1.360794 H -2.848085 2.013145 1.304068

C -2.662583 -3.986766 0.513939 H -0.006529 1.016400 1.874669

C -2.601246 -3.664719 -0.981600 H -1.508952 0.138201 2.109870

C 1.084472 -2.404968 -0.660485 H -2.105264 2.135865 3.686890

C 1.522748 -1.931285 0.611254 H -2.280572 4.615631 4.039232

C 0.424287 -1.979735 1.514669 H -2.145216 4.879047 2.312291

Zr 0.090192 -0.153078 -0.222650 H -4.526832 4.986240 3.090952

C 2.102693 0.039246 -1.742596 H -4.328238 3.662414 1.946706

C 2.349591 0.960171 -0.678327 H -4.425124 3.323639 3.679891

C 1.402327 2.036177 -0.778722 H -0.680564 3.037070 3.196058

C 0.547545 1.749360 -1.862036 H -1.850324 0.597912 -2.837510

C 0.969361 0.518383 -2.453276 H -2.059725 -1.183634 -2.397665

C 1.518258 3.304527 0.021016 H -2.873803 1.267537 -0.697299

C 2.537344 3.173343 1.159125 H -3.098226 -0.507006 -0.230518

C 3.807810 2.462549 0.690378

C 3.517546 1.012670 0.277923 ! Third Insertion of Ethylene to Catalyst

C 2.850234 -1.241796 -2.011482 - Transition State !

C 1.934173 -2.475004 -1.902057 scf done: -1099.001043

C -2.132691 -0.142787 -2.096746 C -1.141431 -3.834213 -1.777285

C -2.698320 0.222675 -0.929210 C -0.343478 -3.010809 -0.799360

C -1.041409 0.876840 1.445504 C -0.812215 -2.716107 0.521097

C -1.795518 2.200242 1.551125 C -2.178956 -3.117156 1.001152

C -1.732803 2.851737 2.939940 C -2.648067 -4.354528 0.222740

C -2.511830 4.166809 3.065129 C -2.573486 -4.117810 -1.287393

C -4.026999 4.024075 2.936020 C 1.036812 -2.657582 -0.875284

H 4.400248 0.566751 -0.193267 C 1.416600 -2.160962 0.408528

H 2.777310 4.169718 1.544032 C 0.276722 -2.198301 1.258459

H 1.855340 4.090159 -0.669787 Zr -0.010985 -0.417606 -0.534792

H 4.564245 2.469701 1.482113 C 2.032003 -0.221972 -1.977129

H 2.098187 2.614942 1.997775 C 2.225468 0.738275 -0.935097

H 0.546804 3.636570 0.400090 C 1.267184 1.791320 -1.109490

H 0.450644 -1.702441 2.562334 C 0.451712 1.453022 -2.210692

H -2.727397 -1.998960 1.372204 C 0.916489 0.214458 -2.746066

H -2.122838 -4.922916 0.708152 C 1.337297 3.088929 -0.352397

H -3.107157 -4.446946 -1.556923 C 2.298461 3.006768 0.839154

H -1.125508 -3.129943 -2.502154 C 3.600011 2.302550 0.454260

H -0.715234 -4.537472 -1.558899 C 3.351629 0.838104 0.067556

H -3.156803 -2.736482 -1.171059 C 2.823314 -1.488800 -2.185649

H -3.700212 -4.153381 0.821191 C 1.938576 -2.743896 -2.078555

H -1.950540 -3.178710 2.405074 C -2.090140 -0.504487 -1.998075

H -0.259317 2.381660 -2.213978 C -2.616913 0.209854 -0.953586

H 2.537029 -1.647172 0.863078 C -1.247928 0.674957 1.081849

H 4.236287 3.006504 -0.161887 C -1.924004 2.018144 1.298942

H 3.324571 0.422628 1.183583 C -1.775578 2.585726 2.718072 C -2.436101 3.956524 2.910210 C -2.258009 -3.782790 -1.575271

C -3.952488 3.965925 2.728093 C 1.240511 -2.595232 -0.303725

H 4.262459 0.397685 -0.352516 C 1.327056 -2.022796 0.999015

H 2.504601 4.017364 1.206304 C 0.021123 -1.993457 1.564115

H 1.707743 3.849246 -1.054436 Zr 0.166989 -0.361762 -0.370232

H 4.316196 2.342846 1.281578 C 2.326136 -0.312378 -1.613497

H 1.825297 2.465254 1.670442 C 2.334534 0.897782 -0.865026

H 0.347839 3.433430 -0.037107 C 1.287766 1.746182 -1.349182

H 0.253942 -1.902817 2.301472 C 0.639387 1.059156 -2.410004

H -2.908962 -2.307550 0.861432 C 1.268908 -0.202141 -2.569017

H -2.021276 -5.213326 0.496591 C 1.123318 3.170545 -0.892756

H -2.963191 -4.987220 -1.826840 C 1.896452 3.441305 0.403702

H -1.160749 -3.388029 -2.779609 C 3.310007 2.858972 0.348296

H -0.611218 -4.789268 -1.893568 C 3.288559 1.329203 0.222316

H -3.239485 -3.282698 -1.542141 C 3.217998 -1.510426 -1.408609

H -3.674102 -4.606052 0.511015 C 2.387613 -2.796126 -1.262412

H -2.149863 -3.321371 2.076651 C -1.911069 -0.082779 -1.185535

H -0.355642 2.055159 -2.611261 C -2.201555 1.252059 -0.465449

H 2.413664 -1.852513 0.697800 C -1.683475 1.325251 0.986971

H 4.062081 2.830658 -0.390278 C -2.122952 2.593762 1.725288

H 3.130348 0.266991 0.979035 C -1.702206 2.634817 3.194435

H 0.524612 -0.283898 -3.625001 C -2.073189 3.933946 3.918582

H 1.328647 -2.847861 -2.982327 C -3.573964 4.194874 4.024840

H 2.567846 -3.641871 -2.028050 H 4.293278 0.951101 0.004068

H 3.322470 -1.465792 -3.161205 H 1.936040 4.520133 0.585422

H 3.617931 -1.536969 -1.434557 H 1.518811 3.819678 -1.686394

H -1.556810 2.759513 0.576842 H 3.874982 3.143291 1.242091

H -2.993580 1.894817 1.089155 H 1.361113 3.005982 1.260763

H -0.159763 0.753195 1.398557 H 0.067318 3.442457 -0.786921

H -1.687113 -0.081233 1.742515 H -0.229513 -1.651029 2.562684

H -2.201018 1.870708 3.436424 H -2.980136 -2.082862 0.659880

H -2.196017 4.315635 3.918451 H -2.273340 -5.018178 0.194844

H -1.980790 4.677929 2.217430 H -2.619371 -4.561937 -2.254545

H -4.366697 4.953782 2.954996 H -0.428630 -3.282882 -2.640910

H -4.250158 3.722524 1.702221 H -0.307747 -4.716880 -1.644536

H -4.439087 3.245457 3.396257 H -2.702013 -2.839373 -1.916219

H -0.708268 2.669023 2.963848 H -3.805449 -4.212891 -0.118684

H -1.771381 0.009329 -2.898128 H -2.487129 -3.261031 1.860086

H -2.287298 -1.565738 -2.089384 H -0.173485 1.441017 -3.013992

H -2.680826 1.290871 -1.002744 H 2.236909 -1.692270 1.487555

H -3.220087 -0.269922 -0.189563 H 3.842579 3.285103 -0.511693

H 3.011392 0.893267 1.194254

! Third Insertion of Ethylene to Catalyst H 1.002395 -0.948719 -3.308673

- Product ! H 1.989631 -3.093747 -2.237712 scf done: -1099.090651 H 3.026364 -3.623006 -0.927878

C -0.728641 -3.701648 -1.673056 H 3.924752 -1.609278 -2.241565

C -0.134245 -2.932082 -0.524805 H 3.822325 -1.355342 -0.509090

C -0.879555 -2.578585 0.635669 H -1.732412 3.475093 1.199585

C -2.323833 -2.948738 0.822300 H -3.215655 2.649126 1.646286

C -2.719662 -4.074312 -0.145235 H -0.562030 1.334509 1.047011 H -2.025968 0.447522 1.551568 C -0.233372 -0.122925 -5.326209

H -2.155593 1.784053 3.723163 C 1.187121 5.312575 -5.630647

H -1.643659 3.900859 4.927491 H -3.007787 -2.912736 -7.613557

H -1.589243 4.779635 3.411253 H 0.123808 1.774661 1.654604

H -3.772075 5.099080 4.609588 H -0.642074 1.967961 0.086137

H -4.040386 4.337580 3.044313 H -0.985480 -4.929930 -4.379238

H -4.089858 3.364076 4.520963 H -3.294235 -0.882340 -6.042614

H -0.613806 2.494054 3.263895 H -0.247496 3.904783 -3.886330

H -2.051564 0.017705 -2.265311 H 1.081656 2.843914 -4.285088

H -2.612586 -0.846171 -0.836772 H -3.249423 2.943146 -5.732203

H -1.791442 2.098234 -1.029988 H -3.616734 1.244696 -5.642117

H -3.286034 1.424796 -0.415253 H -0.827606 -0.154049 -6.249337

H 0.747628 0.296381 -5.571752

! Isomer A Geometry ! H -0.019232 -1.205135 -5.185651 scf done: -1650.680809 H -2.948435 -4.689562 -5.828389

C 1.584896 1.718274 -1.505425 H -1.515531 -4.729015 -6.849896

C 1.252772 0.277759 -1.784731 H -1.520282 -2.236637 -6.976746

C 0.546067 -0.543742 -0.851465 H -4.301420 -2.275455 -5.722041

C 0.079396 -0.038770 0.488217 H -0.168925 -3.596652 -5.174955

C 0.200113 1.487366 0.600942 H 1.612585 3.075608 0.176658

C 1.511577 1.999469 0.001797 H 2.358110 1.516278 0.507166

C 1.695692 -0.559401 -2.838191 H 2.585460 1.940699 -1.891904

C 1.285702 -1.892140 -2.553924 H 0.902372 2.393279 -2.034749

C 0.572547 -1.889123 -1.317679 H 0.714316 -0.508347 1.252714

Zr -0.841498 -0.739120 -3.049153 H -0.942930 -0.362552 0.717751

C -1.875966 1.498508 -2.670794 H 2.288377 -0.247354 -3.689399

Al -1.225206 1.743461 -4.764092 H -2.866662 -1.802113 -0.956258

C 0.120739 3.219411 -4.668217 H -4.064122 -0.678887 -3.090521

C 0.388877 4.042337 -5.944006 H -0.577013 4.360381 -6.364944

C 1.109797 3.214110 -7.009677 H 1.361305 5.915063 -6.530199

C -0.039802 -3.077487 -0.628049 H 0.662607 5.944868 -4.905355

C -0.871341 -3.908084 -1.614005 H 2.167396 5.063967 -5.204147

C -1.740638 -3.019366 -2.462423 H 1.284222 3.795178 -7.922330

C -1.808928 -3.014171 -3.886445 H 2.089465 2.876784 -6.645951

C -2.772010 -2.039669 -4.295576 H 0.538613 2.323444 -7.297680

C -3.281388 -1.426235 -3.124757 H -1.982217 0.717914 -1.869150

C -2.646995 -2.022075 -1.995263 H -1.178440 2.208514 -2.207163

C -1.157109 -3.961609 -4.861033 H 0.738477 -3.698748 -0.168409

C -2.044704 -4.129446 -6.102024 H -0.674549 -2.724905 0.191408

C -2.433641 -2.773623 -6.691851 H -1.486245 -4.637654 -1.073632

C -3.260121 -1.924922 -5.713411 H -0.207159 -4.484555 -2.264809

C -3.279524 2.141276 -2.715075 H 1.518371 -2.767385 -3.150266

C -3.902717 2.365821 -1.332523 H -3.215537 3.107680 -3.232826

C -5.317581 2.942775 -1.400007 H -3.958169 1.530802 -3.320639

C -5.981141 3.082635 -0.029238 H -3.931474 1.407268 -0.791983

C -7.415326 3.625113 -0.107817 H -3.259019 3.031519 -0.741387

C -8.056634 3.775049 1.240109 H -5.289158 3.922672 -1.896154

C -9.161924 3.145978 1.640259 H -5.940075 2.297702 -2.036645

C -2.827753 1.948549 -5.945675 H -5.998132 2.105644 0.472688

C -2.599198 1.832120 -7.460482 H -5.375703 3.743183 0.606829 H -7.393145 4.603678 -0.610288 C -0.921259 -4.925133 -5.445945

H -8.026843 2.964757 -0.735976 C -1.139805 -3.737852 -6.383731

H -7.555012 4.452663 1.933918 C -2.246615 -2.804586 -5.876877

H -9.576447 3.295119 2.634131 C -1.983047 1.279854 -2.969859

H -9.699544 2.461846 0.985675 C -3.403941 1.856197 -3.159698

C -3.876348 1.951995 -8.298889 C -4.005569 2.448277 -1.880715

H -1.889331 2.603276 -7.788857 C -5.430351 2.968704 -2.077898

H -2.119745 0.871831 -7.705852 C -6.061429 3.510965 -0.795091

C -3.630650 1.829825 -9.803728 C -7.504112 3.996330 -0.997533

H -4.589379 1.176983 -7.981473 C -8.120127 4.544350 0.255739

H -4.361197 2.914347 -8.082094 C -9.210422 4.059314 0.850248

C -4.907450 1.891592 -10.642615 C -0.305252 2.867383 -5.270490

H -2.944931 2.626538 -10.125704 C 0.555213 2.987614 -6.537824

H -3.110425 0.882773 -10.010044 C -3.153728 2.881541 -7.721150

C -4.644821 1.760856 -12.150069 H -1.400313 -4.088187 -7.387631

H -5.594002 1.093522 -10.329325 H -0.008892 2.571109 1.166463

H -5.430441 2.837981 -10.446076 H -0.629764 2.456766 -0.472161

C -5.896733 1.842271 -12.972205 H -0.418236 -5.299085 -3.364094

H -3.958132 2.564310 -12.456533 H -2.240810 -1.857919 -6.423488

H -4.129303 0.813934 -12.356422 H -0.282883 -0.540140 -6.244673

C -6.349199 0.885869 -13.783513 H 1.011948 0.195871 -5.292639

H -6.470891 2.765773 -12.873633 H 0.457810 -1.426305 -5.002310

H -7.268906 1.005522 -14.350763 H -1.858813 -5.485675 -5.336217

H -5.812918 -0.052626 -13.915195 H -0.186574 -5.617052 -5.870482

H -0.196954 -3.183274 -6.485864

! Isomer B Geometry ! H -3.224843 -3.260471 -6.084301 scf done: -1650.678494 H 0.594968 -4.104707 -4.151396

C 1.687391 1.733013 -1.755039 H 1.680444 3.430693 -0.416387

C 1.299720 0.279365 -1.727349 H 2.286146 1.948300 0.314028

C 0.451091 -0.268431 -0.719460 H 2.721617 1.832749 -2.101832 C -0.102139 0.550003 0.415905 H 1.069960 2.291970 -2.469814

C 0.128823 2.054323 0.211038 H 0.414622 0.225181 1.330001

C 1.517881 2.349376 -0.360084 H -1.164633 0.343276 0.593836

C 1.775462 -0.796150 -2.519232 H 2.476683 -0.717060 -3.341503 C 1.231934 -2.004652 -2.002522 H -3.193833 -1.659166 -1.339929 C 0.396917 -1.682327 -0.889037 H -3.764788 -1.094371 -3.910387 Zr -0.708330 -0.913040 -3.005964 H -2.089024 0.653561 -2.049059

C 0.094880 -0.397897 -5.221925 H -1.318156 2.088333 -2.634024 Al -1.400094 1.207930 -5.060622 H 0.236243 -3.140561 0.687740

C -2.896883 0.758954 -6.324477 H -1.164245 -2.102614 0.499005

C -3.862036 1.846220 -6.846593 H -1.828945 -4.257442 -0.387999

C -5.022306 1.213546 -7.623658 H -0.327386 -4.446350 -1.273754

C -0.400915 -2.653420 -0.061059 H 1.452772 -3.003250 -2.359724 C -1.069366 -3.707957 -0.955833 H -2.429949 0.288294 -7.207235 C -1.686757 -3.082332 -2.178724 H -3.502431 -0.041934 -5.876946 C -1.348663 -3.376975 -3.534402 H -4.299157 2.377885 -5.988418 C -2.174232 -2.583333 -4.392177 H -5.729481 1.970653 -7.983039 C -2.995636 -1.773175 -3.568315 H -4.651541 0.666081 -8.499552 C -2.697081 -2.079207 -2.208018 H -5.583759 0.504263 -7.004223 C -0.441416 -4.458154 -4.065550 H -3.859085 3.630998 -8.098343 H -2.368170 3.414290 -7.176222 C 0.182641 -0.610932 -5.149728

H -2.689261 2.403516 -8.593268 C 0.264692 -2.617538 0.072712

H -0.999584 3.722235 -5.228403 C -0.343513 -3.779753 -0.723442

H 0.342847 2.993368 -4.390338 C -1.180607 -3.264580 -1.863020

H -3.383732 2.643158 -3.927083 C -1.007277 -3.561440 -3.248795

H -4.076486 1.082601 -3.548684 C -2.037106 -2.894692 -3.987740

H -4.008046 1.678725 -1.094318 C -2.822620 -2.162484 -3.063261

H -3.362062 3.260225 -1.515675 C -2.289557 -2.378047 -1.757603

H -5.428987 3.755705 -2.844872 C -0.071794 -4.559205 -3.885839

H -6.058734 2.158265 -2.473999 C -0.688363 -5.115389 -5.176470

H -6.053274 2.731029 -0.021661 C -1.176139 -3.990134 -6.089021

H -5.449931 4.336441 -0.405344 C -2.306089 -3.180998 -5.438938

H -7.505468 4.776818 -1.773172 C -0.210045 2.776351 -5.323325

H -8.120992 3.173479 -1.380815 C 1.041022 2.740047 -6.212658

H -7.614655 5.403911 0.700532 C -1.895431 1.158064 -2.910808

H -9.609428 4.500347 1.760232 C -3.414939 1.477430 -2.923283

H -9.750101 3.205389 0.443907 C -3.990337 1.532231 -1.503927

C 1.254478 4.343674 -6.677764 C -2.687785 0.632197 -6.272650

H 1.317624 2.194265 -6.547313 C -2.848238 1.623734 -7.436788

H -0.059131 2.816970 -7.433099 C -3.848057 1.165946 -8.504079

C 2.127921 4.467436 -7.927003 C -3.953861 2.113245 -9.700199

H 0.492352 5.136042 -6.688440 C -4.915168 1.621251 -10.783312

H 1.867519 4.527783 -5.783323 C -4.985438 2.554514 -12.000764

C 2.786581 5.839950 -8.070455 C -5.949057 2.078367 -13.047201

H 2.905306 3.689825 -7.908419 C -5.629237 1.764024 -14.302857

H 1.517727 4.264238 -8.818968 C -3.690796 2.801489 -3.640314

C 3.658275 5.967605 -9.328009 H -1.529975 -4.398302 -7.041128

H 2.007922 6.615311 -8.090721 H 0.112398 2.662917 1.097129

H 3.401753 6.050398 -7.185160 H -0.628522 2.436659 -0.477445

C 4.242459 7.338986 -9.495537 H 0.136334 -5.372055 -3.181366

H 4.463311 5.222069 -9.301604 H -2.507674 -2.264756 -6.001119

H 3.039560 5.729676 -10.206589 H -0.297642 -0.842532 -6.108913

C 5.543961 7.624389 -9.541352 H 1.084292 -0.027247 -5.363246

H 3.521333 8.155175 -9.574446 H 0.589764 -1.609601 -4.877942

H 5.901315 8.644322 -9.660230 H -1.529900 -5.773190 -4.923176

H 6.302905 6.847231 -9.466921 H 0.051467 -5.734002 -5.694812

H -0.331366 -3.330933 -6.328615

! Isomer C Geometry ! H -3.236148 -3.765094 -5.482193 scf done: -1650.675372 H 0.901528 -4.106673 -4.120675

C 1.648367 1.911483 -1.936808 H 1.559420 3.644553 -0.647211

C 1.426659 0.428191 -1.839255 H 2.380010 2.262677 0.069647

C 0.722344 -0.172941 -0.749913 H 2.636781 2.106196 -2.366518

C 0.169672 0.621425 0.403270 H 0.923772 2.370907 -2.619161

C 0.223234 2.134528 0.144588 H 0.784034 0.383111 1.282855

C 1.521267 2.554742 -0.549176 H -0.849142 0.311067 0.665352

C 1.967784 -0.614786 -2.627842 H 2.583693 -0.487365 -3.509116

C 1.607010 -1.857214 -2.037402 H -2.700112 -1.987909 -0.832643

C 0.833417 -1.589332 -0.865287 H -3.700912 -1.575279 -3.302534

Zr -0.532273 -1.038003 -2.881062 H -1.741439 0.571557 -1.967899

Al -1.226469 1.087127 -4.968294 H -1.348723 2.076514 -2.649406 H 1.040420 -2.984393 0.756545 ! Isomer A - Second Bimetallic Species

H -0.502179 -2.150076 0.699250 (Propyl chain) !

H -0.947599 -4.416353 -0.066822 scf done: -1729.274912

H 0.454247 -4.414105 1.120678 C -2.922756 -2.342482 -5.905857

H 1.913813 -2.837549 2.382666 C -2.683241 -2.348181 -4.421887

H -0.954074 3.432203 5.803790 C -1.834647 -3.301940 -3.777426

H 0.036722 3.289638 4.382540 C -1.088250 -4.366063 -4.543053

H -3.939680 0.681843 3.467230 C -1.751028 -4.595742 -5.908193

H -4.764994 3.012534 3.658821 C -1.959426 -3.275919 -6.651603

H -3.196751 3.634731 3.126592 C -3.338310 -1.603016 -3.410381

H -3.348233 2.799556 4.680642 C -2.920189 -2.109467 -2.144901

H -5.064355 1.747809 I.526116 C -1.999177 -3.172681 -2.364371

H -3.859045 0.582152 0.972570 Zr -0.898085 -1.004149 -3.049018

H -3.508929 2.319336 0.911183 Al -1.277545 1.523002 -4.697252

H -2.461588 -0.353835 6.705145 C -0.131321 -0.224922 -5.326364

H -3.657274 0.502466 5.770455 C -1.311993 -3.987104 -1.300662

H -3.158981 2.607801 7.057071 C -0.516385 -3.082362 -0.348119

H -1.874589 1.791803 7.920305 C 0.273474 -2.066184 -1.128349

H -3.553705 0.167791 8.860529 C 0.433978 -0.680467 -0.820576

H -4.838705 1.041423 8.043226 C 1.265248 -0.086445 -1.815951

H -4.271277 3.107669 9.354972 C 1.632940 -1.108442 -2.728448

H -2.955363 2.250298 10.139912 C 1.027855 -2.324410 -2.312609

H -4.609459 0.621033 I I.118912 C 0.025696 0.032706 0.441072

H -5.921078 1.504880 10.356062 C 0.427980 1.516386 0.435393

H -5.287902 3.555734 11.658542 C 1.787930 1.750850 -0.225162

H -3.986524 2.663632 12.442167 C 1.776115 1.322245 -1.700102

H -6.988680 1.979314 12.727967 C -1.873858 1.180493 -2.566073

H -6.375611 1.417796 15.013592 C -3.213810 1.947514 -2.620337

H -4.607403 1.845507 14.669976 C -3.777256 2.315311 -1.243363

C 1.581542 4.132787 6.553544 C -5.080463 3.111552 -1.331988

H 1.837396 2.164692 5.716907 C -5.677960 3.462226 0.030903

H 0.828269 2.205956 7.150487 C -6.981209 4.266629 -0.080383

C 2.836223 4.126127 7.427846 C -7.561211 4.636137 1.252723

H 0.790152 4.703847 7.059492 C -8.766235 4.272591 1.692163

H 1.791345 4.673521 5.619212 C -0.191118 3.195973 -4.460112

C 3.335956 5.530310 7.771204 C -0.345137 4.331732 -5.495488

H 3.636249 3.570259 6.917289 C 0.118565 5.673106 -4.915802

H 2.630742 3.576903 8.358054 C -2.895169 1.565652 -5.883498

C 4.599952 5.533485 8.643095 C -2.615682 1.582841 -7.395035

H 2.539012 6.082222 8.289052 C -3.870542 1.575609 -8.274160

H 3.538853 6.086959 6.846343 C -3.559790 1.618817 -9.771556

C 5.043094 6.916824 9.017675 C -4.802448 1.587581 -10.661425

H 5.413573 5.011987 8.122850 C -4.469152 1.646382 -12.159466

H 4.394486 4.959793 9.559337 C -5.688185 1.649520 -13.033390

C 6.215235 7.466089 8.698635 C -5.972262 0.737378 -13.963441

H 4.323359 7.507265 9.588417 C 0.413024 4.037208 -6.790856

H 6.470471 8.479945 8.996869 H -2.348511 -3.462596 -7.657654

H 6.967094 6.921252 8.129867 H 0.439419 1.884007 1.466652

H -0.331398 2.106382 -0.091629

H -1.074482 -5.295702 -3.963873 H -2.874894 -1.327443 -6.313019 H -1.990462 0.722748 -7.680938

H -0.498445 3.592790 -3.478697 H -4.467246 0.679553 -8.048726

H 0.879387 2.970510 -4.346341 H -4.501413 2.434771 -8.005673

H -3.474885 2.464978 -5.627068 H -2.978587 2.525280 -9.994115

H -3.564350 0.723385 -5.648568 H -2.908739 0.771354 -10.032339

H -0.783292 -0.450587 -6.182826 H -5.380824 0.676344 -10.457481

C 1.210118 0.319896 -5.855069 H -5.458592 2.430272 -10.402863

H 0.112668 -1.263625 -4.982103 H -3.885936 2.559926 -12.350854

H -2.718274 -5.094568 -5.763487 H -3.822859 0.801455 -12.430283

H -1.131302 -5.273716 -6.504041 H -6.387742 2.471930 -12.870801

H -0.986946 -2.782762 -6.781632 H -6.876868 0.796138 -14.563550

H -3.955252 -2.681042 -6.068984 H -5.306965 -0.101116 -14.163412

H -0.036168 -4.089946 -4.697701 H 1.024607 1.243180 -6.415037

H 2.059800 2.809121 -0.154950 H 1.856055 0.616977 -5.021561

H 2.562824 1.188710 0.312552 C 1.948181 -0.663084 -6.762203

H 2.781459 1.385745 -2.130015 H 2.889795 -0.235500 -7.123669

H 1.151198 2.016909 -2.273092 H 2.190174 -1.595863 -6.237129

H 0.532725 -0.476623 1.272408 H 1.346380 -0.924740 -7.639871

H -1.046664 -0.072000 0.645603

H 2.301582 -0.992913 -3.572155 ! Isomer A - Third Bimetallic species

H -3.282923 -1.775302 -1.178897 (Pentyl) !

H -4.073407 -0.824410 -3.568908 scf done: -1807.880877

H -1.410665 4.438437 -5.750377 C 1.525427 1.343719 -1.253881

H 0.003488 6.488641 -5.640016 C 1.103246 -0.082035 -1.476778

H -0.453486 5.942964 -4.020577 C 0.274312 -0.788742 -0.552311

H 1.177694 5.630878 -4.630968 C -0.238484 -0.175866 0.723675

H 0.272140 4.836686 -7.527178 C 0.041949 1.332554 0.797789

H 1.490980 3.953963 -6.601196 C 1.419824 1.692752 0.237187

H 0.084309 3.102755 -7.259249 C 1.561638 -1.015801 -2.438099

H -2.060831 0.399496 -1.782907 C 1.028915 -2.295062 -2.113847

H -1.126052 1.826644 -2.091119 C 0.229563 -2.160732 -0.939645

H 0.148709 -3.683791 0.284251 Zr -0.946295 -1.062748 -2.865673

H -1.200737 -2.564608 0.332118 C -0.143604 -0.374845 -5.145621

H -2.046971 -4.575154 -0.738916 C 1.203690 0.131708 -5.701041

H -0.640690 -4.706837 -1.778483 C 1.975629 -0.925486 -6.496702

H 1.148281 -3.291029 -2.787759 C -0.503075 -3.269571 -0.235936

H -3.075286 2.877133 -3.190012 C -1.248557 -4.143768 -1.252837

H -3.962063 1.371464 -3.176366 C -1.989461 -3.286590 -2.242490

H -3.950018 1.395391 -0.665165 C -1.894469 -3.353822 -3.663764

H -3.029147 2.895472 -0.685879 C -2.779612 -2.381133 -4.224518

H -4.900627 4.036571 -1.897486 C -3.398998 -1.695382 -3.150787

H -5.816949 2.538465 -1.913136 C -2.910970 -2.244963 -1.930246

H -5.871811 2.542214 0.598648 C -1.181776 -4.378489 -4.510343

H -4.945417 4.035654 0.615813 C -1.941462 -4.585076 -5.828065

H -6.776627 5.184297 -0.652003 C -2.208923 -3.251321 -6.526015

H -7.720351 3.697091 -0.658097 C -3.109155 -2.329197 -5.690746

H -6.926444 5.247674 1.897157 Al -1.228528 1.433058 -4.576211

H -9.132960 4.573425 2.670352 C -2.791973 1.534528 -5.830598

H -9.435530 3.664899 1.085232 C -2.500358 1.380710 -7.331903

H -2.021927 2.471307 -7.647476 C -3.741856 1.452143 -8.227203 C -3.424422 1.311285 -9.717236 H -1.197377 1.782714 -1.973694

C -4.658398 1.366277 -10.618100 H 0.195880 -3.877111 0.352243

C -4.321199 1.222923 -12.109682 H -1.211946 -2.837541 0.477714

C -5.528436 1.310503 -12.995399 H -1.942366 -4.819429 -0.738891

C -5.948281 0.353014 -13.822784 H -0.537866 -4.780157 -1.789204

C -1.932443 1.150991 -2.485518 H 1.243530 -3.222040 -2.633440

C -3.249057 1.949555 -2.606650 H -3.074954 2.845379 -3.218951

C -3.826208 2.408381 -1.263258 H -4.001446 1.365706 -3.148608

C -5.104910 3.233214 -1.422801 H -4.032289 1.529917 -0.633859

C -5.689535 3.719507 -0.096321 H -3.071824 3.002636 -0.729291

C -6.970470 4.546959 -0.275888 H -4.895933 4.100622 -2.064665

C -7.524888 5.058824 1.020704 H -5.858956 2.635879 -1.954777

C -8.736196 4.779953 1.502658 H -5.906574 2.859603 0.551421

C -0.066082 3.052851 -4.320521 H -4.939411 4.322348 0.434287

C -0.159140 4.195404 -5.354960 H -6.745643 5.399969 -0.933962

C 0.569620 3.854659 -6.655592 H -7.731159 3.946904 -0.791304

C 0.386543 5.508545 -4.782227 H -6.862738 5.705727 1.599829

H -2.678047 -3.419468 -7.500727 H -9.080248 5.183730 2.451543

H -0.041277 1.658259 1.839591 H -9.433436 4.142013 0.961888

H -0.727363 1.881981 0.241241 H -1.797234 2.160535 -7.654205

H -1.104631 -5.322545 -3.960610 H -1.988575 0.425902 -7.530128

H -3.073343 -1.304496 -6.072949 H -4.450942 0.666481 -7.927698

H -0.361441 3.462590 -3.340980 H -4.257237 2.406894 -8.050887

H 0.991587 2.774687 -4.198443 H -2.723792 2.104604 -10.014907

H -3.273007 2.511514 -5.670742 H -2.895100 0.362119 -9.887812

H -3.554710 0.798771 -5.533787 H -5.361366 0.572438 -10.331999

H -0.811597 -0.589424 -5.991997 H -5.187756 2.315540 -10.455566

H 0.072662 -1.417474 -4.805246 H -3.612811 2.018653 -12.385509

H -2.892403 -5.094067 -5.622583 H -3.803783 0.270609 -12.284071

H -1.363580 -5.246134 -6.482131 H -6.096899 2.240650 -12.933337

H -1.249201 -2.757830 -6.725623 H -6.835790 0.478433 -14.437941

H -4.154322 -2.650829 -5.796690 H -5.415560 -0.591669 -13.920422

H -0.151160 -4.072305 -4.736762 H 1.017476 0.992859 -6.353909

H 1.615160 2.760914 0.376895 H 1.835650 0.518591 -4.893421

H 2.196656 1.153181 0.794927 C 3.313097 -0.422690 -7.042215

H 2.551514 1.479988 -1.612228 H 2.155701 -1.803720 -5.856992

H 0.907594 2.039059 -1.834222 H 1.353181 -1.279521 -7.330417

H 0.275977 -0.680685 1.553225 C 4.081101 -1.489831 -7.816506

H -1.306043 -0.374640 0.877225 H 3.135583 0.445274 -7.690782

H 2.250589 -0.805573 -3.245543 H 3.930904 -0.059044 -6.209588

H -3.235217 -1.963997 -0.934314 H 5.033903 -1.101906 -8.191383

H -4.152532 -0.922618 -3.241532 H 4.305250 -2.358695 -7.186138

H -1.218537 4.362929 -5.602653 H 3.508241 -1.847094 -8.679889

H 0.315425 6.326692 -5.509125

H -0.162706 5.814766 -3.884500 ! Isomer A - Fourth Bimetallic species

H 1.443111 5.404360 -4.504097 (Heptyl) !

H 0.466489 4.657409 -7.394609 scf done: -1886.486912

H 1.642864 3.711642 -6.475522 C -2.786147 -2.634160 -5.762684

H 0.184754 2.937226 -7.114600 C -2.763654 -2.498605 -4.266479

H -2.177905 0.369055 -1.719491 C -2.097668 -3.433395 -3.411367 C -1.316832 -4.603614 -3.956431 H 0.938184 2.585621 -4.131748

C -1.786203 -4.935183 -5.380109 H -3.356301 2.131231 -5.648308

C -1.792832 -3.689145 -6.266791 H -3.470095 0.393638 -5.631823

C -3.503995 -1.614905 -3.444533 H -0.592758 -0.786645 -5.858749

C -3.330722 -2.021002 -2.089319 H 0.064451 -1.687393 -4.590244

C -2.479088 -3.161340 -2.062309 H -2.796246 -5.363421 -5.339143

Zr -1.122569 -1.149308 -2.731083 H -1.133745 -5.703083 -5.808116

C -0.054646 -0.620183 -4.911558 H -0.779787 -3.266797 -6.299063

Al -1.247135 1.210059 -4.571728 H -3.805436 -2.937299 -6.039534

C -0.100409 2.848483 -4.383241 H -0.238723 -4.392509 -3.978077

C -0.088952 3.878929 -5.531533 H 1.696902 2.676797 0.329648

C 0.440159 5.235856 -5.053772 H 1.956067 1.061990 0.980821

C -2.050419 -3.915735 -0.831886 H 2.550327 1.038182 -1.409039

C -1.376053 -2.973218 0.174879 H 1.025880 1.789427 -1.842389

C -0.382152 -2.093586 -0.534224 H -0.377633 -0.318939 1.730463

C -0.156821 -0.700572 -0.326499 H -1.781376 0.175435 0.814341

C 0.875656 -0.273680 -1.214745 H 2.090762 -1.416506 -2.698387

C 1.288537 -1.400298 -1.971003 H -3.818083 -1.576299 -1.228703

C 0.522762 -2.520917 -1.553561 H -4.147184 -0.816377 -3.789395

C -0.684914 0.159172 0.790242 H -1.124070 4.034695 -5.872749

C -0.129493 1.592677 0.745439 H 0.435048 5.979581 -5.859739

C 1.331150 1.645537 0.291972 H -0.165011 5.634806 -4.231654

C 1.492074 1.095049 -1.132294 H 1.472356 5.148135 -4.691271

C 1.379009 -0.162518 -5.250191 H 0.691387 4.117583 -7.555958

C 2.168921 -1.211838 -6.038892 H 1.780604 3.262055 -6.459958

C 3.588874 -0.774952 -6.402324 H 0.358804 2.439029 -7.121901

C 4.357648 -1.830616 -7.198584 H -2.292784 0.348585 -1.715570

C -2.779645 1.218067 -5.863147 H -1.240473 1.704424 -1.992272

C -2.472238 1.194644 -7.369303 H -0.884323 -3.549136 0.968835

C -3.729436 1.215940 -8.245464 H -2.127989 -2.349175 0.669324

C -3.444347 1.235950 -9.747910 H -2.913611 -4.411992 -0.373415

C -4.712054 1.267357 -10.602641 H -1.353730 -4.708451 -1.120547

C -4.429176 1.302635 -12.111467 H 0.634339 -3.537081 -1.912793

C -5.678910 1.395350 -12.935813 H -3.053164 2.820188 -3.294160

C -6.077784 0.497605 -13.837115 H -4.052248 1.389566 -3.182706

C -1.998586 1.097083 -2.499959 H -4.070666 1.611730 -0.677083

C -3.273522 1.952831 -2.656787 H -3.033175 3.027235 -0.800404

C -3.822652 2.468294 -1.321361 H -4.810469 4.214782 -2.115770

C -5.056624 3.359134 -1.471473 H -5.849314 2.802961 -1.991465

C -5.589435 3.871151 -0.132309 H -5.839651 3.020516 0.515975

C -6.825540 4.770383 -0.274013 H -4.795349 4.427170 0.385576

C -7.305303 5.310029 1.041085 H -6.573347 5.610759 -0.938239

C -8.512382 5.100524 1.566701 H -7.635654 4.215858 -0.764315

C 0.725737 3.395384 -6.732236 H -6.586503 5.915417 1.597108

H -2.047905 -3.957366 -7.297077 H -8.797046 5.521075 2.527885

H -0.234715 2.043813 1.737651 H -9.265820 4.506157 1.052366

H -0.734007 2.205242 0.065788 H -1.845950 2.056252 -7.636511

H -1.443313 -5.471853 -3.300955 H -1.876330 0.306042 -7.630021

H -2.621596 -1.670654 -6.255293 H -4.352923 0.342604 -8.003503

H -0.485160 3.354949 -3.482704 H -4.330035 2.097527 -7.978906 H -2.824009 2.111298 -9.988289 C -0.095010 -4.731069 4.215373

H -2.844269 0.355023 -10.019145 C -0.171648 -5.509094 3.027904

H -5.333204 0.390476 -10.375226 C -0.791293 -4.719394 2.006767

H -5.313133 2.145704 -10.328086 C -1.068956 -3.444627 2.560107

H -3.789838 2.172043 -12.326825 C -0.635731 -3.443564 3.911501

H -3.857149 0.413082 -12.405228 C 0.148900 -6.969273 2.831392

H -6.300780 2.274940 -12.756931 C -0.755305 -7.559977 1.740304

H -6.999937 0.623391 -14.399088 C -0.719524 -6.717041 0.463677

H -5.493245 -0.395694 -14.051246 C -1.256236 -5.296936 0.696242

H 1.333792 0.759589 -5.839557 C -0.434437 5.108863 -1.636813

H 1.924920 0.104671 -4.338348 C -1.679450 4.413377 -1.067590

H 2.215573 -2.145621 -5.456526 C -1.453082 3.755534 0.297342

H 1.618782 -1.456756 -6.958516 C -2.705999 3.105886 0.886670

H 3.544415 0.157448 -6.982113 C -2.463675 2.425535 2.234350

H 4.144240 -0.535717 -5.483943 C -3.731938 1.806538 2.838693

C 5.782533 -1.410332 -7.561394 C -3.502168 1.177045 4.179965

H 4.393300 -2.766815 -6.622180 C -3.781766 -0.087971 4.501040

H 3.804298 -2.063832 -8.119570 C 0.409091 7.553490 -3.936877

C 6.538399 -2.474176 -8.352427 C 1.581996 7.365101 -4.921478

H 5.748792 -0.477775 -8.140976 C 2.570941 6.310972 -4.415362

H 6.336275 -1.175673 -6.641976 C 2.303261 8.687561 -5.198461

H 7.555036 -2.146835 -8.594608 C 2.251830 -4.522452 0.090473

H 6.619406 -3.410142 -7.786979 C 2.985312 -3.397057 0.035028

H 6.032676 -2.704026 -9.297514 H -1.308661 -7.197872 -0.324000

H 2.690666 1.106637 5.264738

! First Insertion when the Co-Catalyst H 2.138605 0.471771 3.722055 Dissociates - Adduct ! H 0.011794 -7.508715 3.774683 scf done: -1729.239564 H -1.016956 -4.641022 -0.149702

C 4.335591 -1.066439 3.097697 H -0.294723 8.290581 -4.353246

C 3.649580 -2.303102 3.607015 H 0.791386 8.006745 -3.008774

C 2.660836 -2.272363 4.632619 H -2.787445 4.929618 -4.343856

C 2.230300 -1.000209 5.310088 H -1.468539 3.894489 -4.799890

C 2.767220 0.246548 4.591488 H 1.875296 -0.834166 1.666851

C 4.214630 0.065607 4.128040 H 0.356330 -0.830266 2.575011

C 3.937348 -3.663628 3.328659 H 0.411566 -1.556759 0.974029

C 3.147901 -4.474406 4.190502 H -1.785328 -7.611941 2.116260

C 2.357384 -3.616947 5.009554 H -0.445463 -8.587554 1.523475

Zr 1.472640 -3.517255 2.670946 H 0.313276 -6.678928 0.092741

C 0.985592 -1.429030 1.905602 H -2.353839 -5.333932 0.733202

Al -0.597133 5.893189 -3.466284 H 1.200170 -7.123576 2.547257

C -1.772642 4.954235 -4.775772 H 4.590705 0.997397 3.693047

C -1.838519 5.505552 -6.206805 H 4.852895 -0.159679 4.992790

C -2.782598 4.730523 -7.131674 H 5.388862 -1.290859 2.894244

C -2.830643 5.277727 -8.559420 H 3.902026 -0.734459 2.144959

C -3.760418 4.492642 -9.485511 H 2.622042 -1.026712 6.337047

C -3.792113 5.041676 -10.919597 H 1.140021 -0.941759 5.408675

C -4.724287 4.281818 -11.815987 H 4.681289 -4.025729 2.628026

C -4.367651 3.622421 -12.918695 H -0.745040 -2.619581 4.606682

C 1.405863 -4.063739 6.086261 H -1.559560 -2.623256 2.054602

C 0.463757 -5.148874 5.548210 H 1.174986 7.004437 -5.877635 H 3.106528 8.568156 -5.936072 C 0.297436 -0.941390 1.603049

H 1.609657 9.443925 -5.582294 C 0.745573 0.336708 0.881667

H 2.751909 9.087030 -4.280202 C 2.185484 0.222987 0.375478

H 3.412719 6.176106 -5.104520 C 1.925490 -3.484746 -0.601519

H 2.983844 6.594447 -3.439054 C 1.168496 -4.343839 0.237578

H 2.095922 5.325708 -4.296881 C 0.416748 -3.540564 1.149157

H 0.397269 4.383663 -1.675695 Zr -0.555922 -3.246248 -1.134356

H -0.089220 5.887449 -0.940261 C -0.793248 -1.253221 -2.317406

H 1.960399 -4.434145 6.956962 Al -2.435826 5.654206 -6.939527

H 0.825351 -3.203487 6.434249 C -3.584110 4.676718 -8.244511

H -0.348909 -5.336903 6.260672 C -3.646813 5.209993 -9.682611

H 1.004461 -6.094617 5.439734 C -4.575780 4.413901 -10.604855

H 3.184260 -5.556081 4.256913 C -4.619104 4.944108 -12.039159

H -2.501144 5.138810 -0.975791 C -5.534263 4.139343 -12.962957

H -2.039302 3.649980 -1.772239 C -5.560650 4.672017 -14.403326

H -0.658174 3.000773 0.202388 C -6.478748 3.893416 -15.298177

H -1.069755 4.509712 0.999618 C -6.106770 3.223930 -16.389658

H -3.489388 3.868483 1.002589 C -0.534671 -4.049927 2.200579

H -3.105323 2.369200 0.174536 C -1.510812 -5.079994 1.609216

H -1.700051 1.643492 2.119781 C -2.094239 -4.588316 0.309248

H -2.047387 3.156596 2.941571 C -2.143142 -5.293161 -0.932017

H -4.487729 2.599375 2.944481 C -2.769217 -4.456800 -1.905142

H -4.154268 1.065084 2.148251 C -3.081342 -3.225449 -1.278366

H -3.079551 1.832121 4.944826 C -2.677664 -3.305735 0.086107

H -3.611135 -0.473652 5.503468 C -1.817530 -6.737222 -1.216359

H -4.219581 -0.777051 3.780338 C -2.771046 -7.271030 -2.294969

H -2.150128 6.559701 -6.187484 C -2.744468 -6.391016 -3.545716

H -0.833619 5.505429 -6.652694 C -3.196760 -4.946780 -3.261892

H -2.474175 3.674963 -7.155882 C -2.255759 4.884882 -5.104364

H -3.794828 4.738950 -6.701560 C -3.491848 4.191207 -4.513999

H -3.146605 6.330751 -8.535491 C -3.244328 3.546119 -3.146589

H -1.815285 5.277025 -8.981889 C -4.484511 2.895959 -2.531272

H -3.449603 3.439510 -9.513914 C -4.215304 2.230691 -1.181063

H -4.779171 4.498602 -9.072684 C -5.466834 1.607790 -0.546588

H -4.104311 6.096416 -10.883986 C -5.206654 0.994980 0.796900

H -2.780069 5.029704 -11.344258 C -5.471009 -0.268762 1.136815

H -5.773643 4.273548 -11.513805 C -1.463660 7.332033 -7.416927

H -5.094084 3.085275 -13.523608 C -0.285630 7.156818 -8.398054

H -3.334515 3.599551 -13.261731 C 0.712631 6.113010 -7.888741

H 2.593661 -2.487714 -0.413667 C 0.421926 8.487052 -8.672802

H 4.011671 -3.365752 0.389357 C 0.199442 -4.090768 -3.274864

H 2.675528 -5.452579 0.469332 C 0.210545 -2.749786 -3.655224

H 1.261798 -4.570368 -0.354657 H -3.387326 -6.816790 -4.322926

H 0.647840 1.187549 1.563533

! First Insertion when the Co-Catalyst H 0.079078 0.540543 0.032419 Dissociates - Transition State ! H -1.910556 -7.327194 -0.298494 scf done: -1729.224728 H -2.860425 -4.274213 -4.061013

C 2.325531 -0.876611 -0.687151 H -2.178667 8.055115 -7.838367

C 1.653429 -2.143394 -0.227325 H -1.090757 7.796106 -6.490333

C 0.716928 -2.177360 0.854470 H -4.601890 4.640976 -7.820408 H -3.262190 3.622016 -8.253000 H -3.600755 4.948807 -12.454281

H -0.030925 -0.505799 -2.535297 H -5.212977 3.089065 -12.977290

H -1.124548 -1.063904 -1.259447 H -6.556012 4.139945 -12.557581

H -1.672297 -1.080501 -2.939329 H -5.883000 5.724055 -14.381860

H -3.790220 -7.309079 -1.888719 H -4.545406 4.664864 -14.820362

H -2.494378 -8.298228 -2.554596 H -7.530606 3.879712 -15.005050

H -1.726873 -6.400996 -3.957678 H -6.822968 2.672980 -16.994355

H -4.293818 -4.903208 -3.285312 H -5.070503 3.206150 -16.723432

H -0.781703 -6.862179 -1.560898 H -0.516214 -2.377434 -4.368816

H 2.518225 1.179083 -0.041504 H 1.135907 -2.184013 -3.604458

H 2.849336 -0.000216 1.221077 H 1.138082 -4.572102 -3.012796

H 3.383346 -1.080472 -0.888156 H -0.575312 -4.735852 -3.673772

H 1.903191 -0.518589 -1.635298

H 0.765100 -0.977946 2.597191 ! First Insertion when the Co-Catalyst

H -0.783857 -0.922345 1.785907 Dissociates - Product !

H 2.629019 -3.800108 -1.362827 scf done: -1729.265015

H -2.820275 -2.533516 0.833581 C 4.199105 -0.920212 2.984336

H -3.594938 -2.389597 -1.737503 C 3.530720 -2.171558 3.496844

H -0.685979 6.791754 -9.355301 C 2.592987 -2.164162 4.579839

H 1.227264 8.376965 -9.409531 C 2.182521 -0.899825 5.285031

H -0.279382 9.236117 -9.056914 C 2.592181 0.344366 4.485995

H 0.864966 8.890638 -7.753618 C 4.033672 0.232785 3.984394

H 1.557718 5.985868 -8.575261 C 3.782179 -3.524811 3.151903

H 1.119893 6.400838 -6.911315 C 3.007423 -4.348756 4.013581

H 0.247022 5.122781 -7.771612 C 2.273306 -3.511672 4.910551

H -1.422926 4.160971 -5.147276 Zr 1.323142 -3.278140 2.610068

H -1.904537 5.670010 -4.418350 C 1.578685 -1.432046 0.383389

H 0.020159 -4.492794 3.036849 Al -0.558778 5.703225 -3.294113

H -1.093454 -3.205409 2.617433 C -1.716540 4.744730 -4.604544

H -2.310223 -5.296384 2.328474 C -1.779276 5.291062 -6.037758

H -0.990106 -6.027064 1.434486 C -2.711947 4.506143 -6.965782

H 1.185899 -5.428027 0.216372 C -2.754356 5.048622 -8.395519

H -4.313877 4.915338 -4.416699 C -3.672735 4.254729 -9.325467

H -3.859332 3.421181 -5.207479 C -3.697469 4.798971 -10.761523

H -2.447064 2.794079 -3.247042 C -4.618292 4.030451 -11.662272

H -2.853557 4.307919 -2.456875 C -4.248762 3.368293 -12.759043

H -5.269420 3.655687 -2.409183 C 1.306480 -3.976689 5.968538

H -4.892386 2.150887 -3.229784 C 0.306187 -4.993604 5.395108

H -3.447261 1.453026 -1.301231 C -0.256221 -4.516667 4.079811

H -3.791771 2.971563 -0.488698 C -0.322251 -5.256058 2.855795

H -6.226592 2.395753 -0.434742 C -0.904970 -4.428386 1.853284

H -5.896958 0.855661 -1.220489 C -1.189323 -3.170281 2.451629

H -4.777174 1.662116 1.547340 C -0.809763 -3.228430 3.821143

H -5.282566 -0.640938 2.141178 C 0.013624 -6.703216 2.607698

H -5.919232 -0.968135 0.432645 C -0.859554 -7.250929 1.470404

H -3.969811 6.260819 -9.677630 C -0.781970 -6.357365 0.231600

H -2.638851 5.215745 -10.121468 C -1.315604 -4.942420 0.502412

H -4.255975 3.361495 -10.614612 C -0.371296 4.908907 -1.470068

H -5.591142 4.416557 -10.182115 C -1.607283 4.210777 -0.884984

H -4.945670 5.994095 -12.029573 C -1.359520 3.550972 0.475394 C -2.601720 2.900240 1.085825 H 3.008123 -5.433378 4.019530

C -2.336961 2.226430 2.432597 H -2.428117 4.934954 -0.778403

C -3.592406 1.606980 3.062590 H -1.977106 3.448840 -1.586019

C -3.339320 0.991638 4.406242 H -0.565183 2.796859 0.365847

C -3.608632 -0.271894 4.743253 H -0.964714 4.304461 1.171942

C 0.413781 7.385283 -3.754862 H -3.384064 3.661778 1.212437

C 1.591196 7.218295 -4.738241 H -3.011800 2.161035 0.382515

C 2.590383 6.171189 -4.237639 H -1.572755 1.444894 2.309090

C 2.297609 8.551042 -5.003495 H -1.909817 2.961283 3.129151

C 2.066468 -3.949769 0.573429 H -4.349101 2.397942 3.173366

C 2.517429 -2.589097 0.003893 H -4.023761 0.857910 2.386148

H -1.349449 -6.801316 -0.592835 H -2.912637 1.657103 5.159796

H 2.473992 1.233390 5.113534 H -3.427583 -0.645458 5.748472

H 1.915253 0.482093 3.629702 H -4.055514 -0.969290 4.036304

H -0.140822 -7.283515 3.523804 H -2.098909 6.342831 -6.023104

H -1.014061 -4.257959 -0.299587 H -0.771886 5.297334 -6.477906

H -0.301174 8.112274 -4.169570 H -2.395896 3.452748 -6.984694

H 0.787380 7.840774 -2.824309 H -3.726964 4.508881 -6.542212

H -2.733643 4.710894 -4.178593 H -3.077323 6.099609 -8.376885

H -1.400625 3.688378 -4.623204 H -1.736245 5.053292 -8.811220

H 1.894286 -0.484359 -0.064699 H -3.355276 3.203457 -9.348298

H 1.588655 -1.192125 1.469629 H -4.694399 4.255807 -8.919884

H 0.544848 -1.613031 0.069716 H -4.016276 5.851897 -10.731671

H -1.899950 -7.319945 1.814526 H -2.682312 4.791687 -11.178763

H -0.539877 -8.268281 1.221885 H -5.670101 4.017861 -11.368917

H 0.262210 -6.305940 -0.101229 H -4.966948 2.824448 -13.367793

H -2.414213 -4.958725 0.481905 H -3.212629 3.349698 -13.093182

H 1.071479 -6.824067 2.336719 H 2.565922 -2.624273 -1.093072

H 4.349686 1.170426 3.516105 H 3.531238 -2.343944 0.341356

H 4.698089 0.069444 4.842917 H 2.877932 -4.683545 0.531444

H 5.261152 -1.126355 2.810725 H 1.247466 -4.339536 -0.041213

H 3.792421 -0.619341 2.010946

H 2.684828 -0.880700 6.262398 ! First Insertion when the Co-Catalyst

H 1.107958 -0.885510 5.503914 does not dissociate - Adduct !

H 4.475116 -3.872709 2.396659 scf done: -1729.242794

H -0.933325 -2.433091 4.547528 C 3.665587 1.507892 1.921111

H -1.674327 -2.330393 1.965529 C 3.089650 0.161272 2.258081

H 1.190353 6.860286 -5.697937 C 2.085841 -0.011372 3.258619

H 3.102169 8.447112 -5.741933 C 1.563282 1.124791 4.097704

H 1.595366 9.302521 -5.381118 C 2.081712 2.494737 3.627942

H 2.741323 8.947902 -4.081706 C 3.528235 2.441235 3.132125

H 3.434614 6.049061 -4.926093 C 3.514855 -1.126494 1.844993

H 2.998808 6.452285 -3.258726 C 2.784301 -2.092677 2.586200

H 2.125225 5.180024 -4.126732 C 1.890701 -1.409674 3.466380

H 0.459569 4.183672 -1.526197 Zr 1.063859 -1.159255 1.127702

H -0.015714 5.683984 -0.774916 C 0.080777 1.040248 0.770712

H 1.848428 -4.415967 6.815022 Al 0.701680 0.588385 -1.283688

H 0.768019 -3.110226 6.366525 C 2.050776 -1.099946 -1.081250

H -0.501805 -5.173222 6.114602 C 0.925383 -2.063019 4.420383

H 0.802679 -5.957376 5.243444 C 0.246561 -3.271671 3.755979 C -0.213911 -2.937586 2.360574 H 0.168870 -1.332539 4.726580

C 0.206339 -3.570413 1.149100 H -0.600755 -3.609919 4.363280

C -0.470566 -2.948280 0.052132 H 0.946920 -4.111124 3.709533

C -1.277785 -1.909771 0.581925 H 2.920489 -3.165991 2.535120

C -1.126639 -1.906506 1.998604 H -0.270554 -0.550940 -3.316891

C 1.045035 -4.813438 0.976717 H -1.422303 -0.733726 -2.027610

C 0.635537 -5.555408 -0.302318 C -3.673721 1.497455 -4.722465

C 0.615313 -4.610583 -1.504075 H -2.166496 -0.034701 -4.948977

C -0.435104 -3.503412 -1.345178 H -3.265472 -0.299089 -3.606612

C 6.382753 -3.426214 -0.709919 H 2.234930 2.622193 -0.839189

C 6.713310 -2.188538 -1.075098 H -1.118462 2.381467 -0.446343

C -1.251876 1.744341 0.439870 H -2.012714 1.006386 0.160817

C -1.782762 2.626307 1.575391 H -1.942423 2.007932 2.471165

C -3.083969 3.344839 1.216021 H -1.018382 3.368110 1.843986

C -3.612132 4.237708 2.339402 H -2.924142 3.953301 0.314882

C -4.917683 4.956478 1.970729 H -3.849597 2.602080 0.950757

C -5.410528 5.867839 3.055677 H -3.777054 3.637274 3.244194

C -6.582920 5.754894 3.680148 H -2.848576 4.983357 2.601331

C -0.774636 0.010195 -2.511107 H -4.746932 5.543225 1.055669

C -1.666484 1.075982 -3.166032 H -5.692851 4.218173 1.729261

C -2.695202 0.480254 -4.133910 H -4.735090 6.676244 3.342967

C 1.819537 2.183437 -1.758680 H -6.883395 6.448530 4.461387

H 1.125588 2.948982 -2.143794 H -7.290439 4.966754 3.427860

C 2.960698 2.009461 -2.780661 H 3.645317 1.231597 -2.407161

C 3.777560 3.297085 -2.930931 C 2.443589 1.551235 -4.146145

H 0.411019 -5.167405 -2.424285 H 6.410342 -1.774996 -2.034681

H 1.990942 3.208844 4.453100 H 7.323010 -1.548823 -0.440578

H 1.446009 2.878303 2.821158 H 6.708374 -3.848783 0.238243

H 0.924418 -5.461581 1.851281 H 5.796517 -4.075566 -1.356996

H -0.285336 -2.713665 -2.087215 H 3.264013 1.401313 -4.857087

H 3.057394 -0.672782 -1.127975 H 1.888673 0.607524 -4.082923

H 2.190904 -2.113409 -0.643500 H 1.767614 2.298673 -4.579203

H 1.771723 -1.381913 -2.106873 H 4.611966 3.167731 -3.630960

H -0.359082 -5.999685 -0.165392 H 3.151446 4.114270 -3.310146

H 1.330063 -6.383098 -0.479244 H 4.195924 3.621197 -1.971109

H 1.613394 -4.167784 -1.626922 H -2.203909 1.645228 -2.395231

H -1.431249 -3.918763 -1.551009 H -1.049071 1.809534 -3.702382

H 2.115988 -4.576226 0.920502 C -4.709299 0.863165 -5.652450

H 3.867094 3.446703 2.861340 H -4.192835 2.016341 -3.903430

H 4.185871 2.090891 3.938495 H -3.117231 2.272637 -5.268406

H 4.715375 1.396977 1.629450 C -5.728758 1.866850 -6.209736

H 3.152080 1.956761 1.061158 H -4.195070 0.366594 -6.487250

H 1.903929 0.942725 5.126138 H -5.249487 0.071997 -5.114762

H 0.467603 1.130322 4.149216 C -6.718661 1.231723 -7.141164

H 4.290575 -1.339129 1.118153 H -6.260068 2.354005 -5.382121

H -1.646896 -1.252062 2.689245 H -5.185418 2.660275 -6.744626

H -1.946311 -1.273824 0.018100 C -8.037798 1.188027 -6.952241

H -0.115725 0.553055 1.763705 H -6.298557 0.762981 -8.033577

H 0.825906 1.804945 1.019489 H -8.701726 0.705253 -7.665065

H 1.440906 -2.373910 5.337953 H -8.505593 1.638965 -6.078435 H 0.803876 -0.070673 -4.962898

! First Insertion when the co-catalyst H -0.165007 -0.700310 -6.457081 does not dissociate - Transition State ! H -3.325137 -6.008124 -3.513599 scf done: -1729.118836 H -1.899474 -6.892652 -4.049087

C 2.185756 1.040681 -2.685187 H -1.355824 -5.111020 -5.676927

C 1.479909 -0.205591 -2.225146 H -4.088720 -3.851684 -5.219252

C 0.519322 -0.189597 -1.167910 H -0.410825 -5.113730 -3.252567

C 0.181112 1.054325 -0.391010 H 2.702954 2.977918 -1.870996

C 0.858163 2.315609 -0.956322 H 2.908458 1.646313 -0.736758

C 2.252548 2.042582 -1.522999 H 3.189662 0.787560 -3.042849

C 1.743109 -1.558616 -2.543804 H 1.665631 1.513769 -3.529008

C 0.944607 -2.381217 -1.702196 H 0.528270 0.888270 0.638076

C 0.186047 -1.533374 -0.840006 H -0.901221 1.210495 -0.314077

Zr -0.742039 -1.430297 -3.182963 H 2.473214 -1.908649 -3.262686

C -1.670497 1.045959 -3.462763 H -3.179753 -0.939558 -1.344007

Al -1.348910 1.185000 -5.610611 H -3.820869 -1.163125 -3.954722

C 0.433316 0.066503 -5.976402 H -1.643933 0.454047 -2.515991

C -0.746910 -1.997906 0.243003 H -0.929917 1.822012 -3.223076

C -1.586308 -3.179463 -0.260000 H -0.181448 -2.282379 1.139381

C -2.123605 -2.889288 -1.633358 H -1.401615 -1.172318 0.540732

C -1.988576 -3.703006 -2.794878 H -2.410532 -3.384808 0.433127

C -2.679646 -3.070188 -3.873854 H -0.976810 -4.087707 -0.294191

C -3.205349 -1.850989 -3.389640 H 0.966638 -3.464082 -1.665327

C -2.864745 -1.734251 -2.009585 H -2.789349 -0.797482 -6.503553

C -1.455014 -5.104700 -2.912234 H -3.808162 0.559510 -6.092754

C -2.312325 -5.886906 -3.919350 C -4.344121 0.426131 -10.250673

C -2.372734 -5.170038 -5.269519 H -4.099738 -1.078688 -8.718706

C -2.995166 -3.764915 -5.171461 H -5.107493 0.276085 -8.237480

C 0.330793 -2.758496 -5.022106 H -0.928060 3.596275 -4.803498

C 1.216601 -2.050470 -5.866058 H -3.206541 2.387842 -4.247670

C -3.078331 1.687692 -3.408990 H -3.845170 0.919544 -3.561103

C -3.376955 2.450720 -2.113772 H -3.232571 1.780361 -1.252977

C -4.792352 3.028861 -2.063617 H -2.645475 3.261890 -1.995522

C -5.092694 3.783853 -0.768237 H -4.941194 3.701244 -2.919940

C -6.524674 4.334652 -0.709351 H -5.520965 2.214469 -2.185802

C -6.804916 5.099569 0.550205 H -4.930925 3.120976 0.092792

C -7.742714 4.788377 1.445320 H -4.380080 4.612653 -0.654540

C -2.863413 0.299539 -6.595018 H -6.682621 4.993749 -1.576098

C -2.993063 0.664460 -8.082281 H -7.243574 3.511135 -0.807419

C -4.190132 0.015920 -8.785295 H -6.173149 5.971999 0.729085

C -1.006041 3.162764 -5.812965 H -7.896372 5.382742 2.342473

H -1.906336 3.624748 -6.250183 H -8.398370 3.929715 1.309873

C 0.215911 3.607541 -6.637036 H 1.110548 3.107780 -6.231574

C 0.451976 5.118303 -6.529772 C 0.083703 3.199623 -8.105865

H -2.951589 -5.762118 -5.985670 H 1.146819 -2.133871 -6.945857

H 0.911784 3.071042 -0.165453 H 2.206415 -1.770972 -5.515350

H 0.237318 2.748516 -1.749534 H 0.829346 -3.355995 -4.254128

H -1.469191 -5.593713 -1.932869 H -0.452147 -3.298649 -5.547476

H -2.715300 -3.155304 -6.039186 H 0.967644 3.484900 -8.688473

H 1.145847 0.563406 -6.632645 H -0.051660 2.117310 -8.220880 H -0.784298 3.686854 -8.567094 C -1.383544 2.644813 2.040866

H 1.340651 5.432655 -7.091053 C -2.628361 3.384916 2.533355

H -0.405048 5.675312 -6.928603 C -2.699691 3.512968 4.055303

H 0.590408 5.429828 -5.487923 C -3.946822 4.265290 4.541901

H -3.075237 1.755430 -8.186632 C -3.986511 4.423526 6.033118

H -2.075907 0.388814 -8.624890 C -4.933351 3.935629 6.834854

C -5.547546 -0.217109 -10.940560 C -0.917346 0.747994 -3.178533 H -4.434215 1.520096 -10.311337 C -1.499233 1.260369 -4.505179

H -3.428241 0.168068 -10.802114 C -2.208513 0.173973 -5.318763

C -5.714617 0.222229 -12.402567 C 0.757651 3.830033 -2.647507

H -5.451089 -1.311433 -10.898890 H 0.133295 4.211768 -3.470478 H -6.464232 0.028336 -10.387586 C 2.236563 3.883264 -3.090069

C -6.863732 -0.455223 -13.088285 C 2.695261 5.328034 -3.311213 H -5.845511 1.310772 -12.450166 H -0.655321 -5.329038 -1.779267

H -4.784653 -0.005376 -12.945351 H 2.537129 3.060979 4.274622 C -7.926907 0.162095 -13.604089 H 1.997292 2.460937 2.716482

H -6.807411 -1.544186 -13.147550 H 0.002078 -5.471898 2.483898 H -8.730864 -0.389737 -14.084919 H -0.682117 -2.754193 -1.601607 H -8.032000 1.245238 -13.569376 H 3.877891 0.577732 -2.058387

H 2.628783 0.846863 -0.841003

! First Insertion when the Co-Catalyst H 2.211021 0.118486 -2.411187 does not dissociate - Product ! H -1.465293 -5.812607 0.554926 scf done: -1729.261417 H 0.073669 -6.596029 0.213362

C 4.085198 0.760625 2.168522 H 0.799635 -4.603590 -1.117168

C 3.265006 -0.417063 2.629752 H -2.075397 -3.597884 -0.963560

C 2.245352 -0.305185 3.627220 H 1.315573 -4.920297 1.458476

C 1.919145 0.993175 4.314363 H 4.490972 2.790916 2.795123

C 2.574398 2.190388 3.612012 H 4.596550 1.606446 4.092477

C 4.018574 1.891679 3.203587 H 5.121352 0.442058 2.010821

C 3.416210 -1.790227 2.317168 H 3.737428 1.136795 1.196530

C 2.493151 -2.524937 3.110983 H 2.299989 0.925147 5.343132

C 1.768342 -1.611142 3.934679 H 0.837568 1.145486 4.413502

Zr 1.051851 -1.320940 1.565444 H 4.133553 -2.213165 1.626163

C -0.044093 1.823055 -0.034464 H -1.606021 -0.777884 3.105564

Al 0.015955 2.084623 -2.035926 H -1.924508 -0.862756 0.430034

C 2.970462 0.151288 -1.618861 H -0.070891 0.742924 0.229152

C 0.675874 -1.996794 4.894122 H 0.857678 2.261008 0.418411

C -0.206709 -3.094214 4.274834 H 1.101845 -2.344111 5.843936

C -0.585387 -2.747161 2.858964 H 0.068423 -1.117703 5.135235

C -0.314815 -3.512192 1.678183 H -1.106292 -3.243281 4.883071

C -0.850856 -2.814175 0.554214 H 0.332314 -4.046461 4.281122

C -1.398236 -1.595782 1.030218 H 2.391555 -3.603455 3.123977

C -1.254919 -1.565151 2.447230 H -0.221678 -0.081003 -3.388910

C 0.222526 -4.915751 1.566016 H -1.718824 0.290541 -2.576585

C -0.403208 -5.620289 0.353052 C -2.770948 0.665870 -6.652977

C -0.264379 -4.778825 -0.917130 H -1.504602 -0.650982 -5.502144

C -1.000182 -3.435999 -0.804483 H -3.022802 -0.252322 -4.714909

C 1.975647 -1.909667 -0.449531 H 0.609694 4.538410 -1.817313

C 3.219534 -1.250088 -1.065534 H -1.332073 3.558178 0.109118

C -1.295918 2.535804 0.515669 H -2.202177 2.039513 0.139674 H -1.368085 1.634341 2.478318 C 0.864777 -3.401902 -0.488758

H -0.485855 3.159452 2.411448 Zr -1.175715 -2.066959 -1.099341

H -2.648865 4.387881 2.084618 C -2.138280 -1.417384 1.121326

H -3.527808 2.869697 2.167849 C -2.359946 -0.222395 0.466507

H -2.688008 2.514082 4.513552 C 0.639830 -4.873804 -0.273546

H -1.800934 4.029720 4.420669 C -0.285131 -5.435181 -1.363514

H -3.959448 5.260505 4.072842 C -1.484213 -4.547659 -1.566554

H -4.851058 3.746260 4.199627 C -1.879908 -3.912313 -2.781912

H -3.158372 4.981830 6.474490 C -3.096269 -3.192771 -2.534762

H -4.903559 4.086543 7.911052 C -3.407780 -3.332210 -1.164996

H -5.781243 3.375381 6.444235 C -2.414322 -4.157783 -0.560867

H 2.860342 3.463392 -2.285347 C -1.306140 -4.073070 -4.169694

C 2.478637 3.050462 -4.350873 C -2.386088 -3.831208 -5.233422

H 3.591312 -1.870613 -1.894021 C -3.162634 -2.541065 -4.962547

H 4.044610 -1.204181 -0.344501 C -3.939094 -2.628061 -3.643981

H 2.161840 -2.991022 -0.349067 C -1.627841 0.111527 -1.820717

H 1.153481 -1.842503 -1.180311 C -2.572547 1.280363 -2.053455

H 3.531837 3.075269 -4.652967 C -3.998828 0.952393 -2.493622

H 2.204439 1.997272 -4.211884 C -4.902367 2.186651 -2.528115

H 1.887137 3.435125 -5.190592 C -6.331060 1.887113 -2.982572

H 3.751222 5.376286 -3.603035 C -7.233193 3.129569 -2.985484

H 2.108920 5.806021 -4.105685 C -8.649117 2.823982 -3.376126

H 2.572381 5.928684 -2.403089 C -9.292370 3.351914 -4.417646

H -2.207873 2.079398 -4.314235 Al -0.472221 5.192207 -7.615585

H -0.699318 1.699075 -5.117155 C -0.232196 3.355051 -6.865720

C -3.488370 -0.426790 -7.446389 C 1.190610 2.941955 -6.468525

H -3.466027 1.498126 -6.471438 C 1.281130 1.537127 -5.870896

H -1.954347 1.080439 -7.261254 C -2.277026 5.747850 -8.252517

C -4.042841 0.065237 -8.790927 C -3.336020 4.646127 -8.398377

H -2.796931 -1.262557 -7.624158 C -4.703132 5.158104 -8.862438

H -4.313213 -0.835939 -6.847635 C -5.754364 4.058100 -9.015461

C -4.717750 -1.019521 -9.576998 C -7.114740 4.575668 -9.484190

H -4.745430 0.891512 -8.623285 C -8.162338 3.464554 -9.643188

H -3.211075 0.476711 -9.382330 C -9.480615 3.969862 -10.149766

C -5.996085 -1.014612 -9.955822 C -10.646851 3.859037 -9.513078

H -4.093523 -1.876329 -9.839541 C 1.032499 6.499609 -7.591357

H -6.428135 -1.836037 -10.521979 C 1.079722 7.522850 -8.741476

H -6.658778 -0.184071 -9.718001 C 1.261459 6.828001 -10.093526

C 2.179094 8.568126 -8.527342

! Chain Shuttle Ethylene Insertion - H -3.861119 -2.338545 -5.781006 Transition State ! H 1.612857 -1.428996 3.732788 scf done: -1807.822298 H 0.209593 -0.755656 2.932418

C 1.437915 0.128699 0.625551 H -0.880672 -5.076347 -4.282300

C 1.152024 -1.132357 -0.141862 H -4.374249 -1.662884 -3.373073

C 0.911558 -2.384481 0.505990 H 0.967925 7.037478 -6.629619

C 1.007557 -2.560561 1.998756 H 1.990383 5.958806 -7.543358

C 1.184566 -1.225697 2.745946 H -2.167226 6.283974 -9.207834

C 2.062191 -0.232631 1.981291 H -2.644228 6.519285 -7.554179

C 1.257740 -1.379181 -1.529894 H -0.641700 2.631043 -7.588681

C 1.076134 -2.771312 -1.752830 H -0.900395 3.269348 -5.991445 H -3.085964 -4.677109 -5.242514 H -8.306818 2.949087 -8.684920

H -1.919396 -3.796957 -6.223282 H -9.455389 4.474826 -11.117607

H -2.462042 -1.693894 -4.937586 H -11.568091 4.252538 -9.935542

H -4.788766 -3.312025 -3.781449 H -10.725525 3.365753 -8.545545

H -0.478219 -3.371515 -4.341624 H 1.851075 2.995907 -7.344381

H 2.205217 0.675518 2.576262 H 1.602161 3.661432 -5.747460

H 3.057490 -0.665604 1.816710 H 2.312502 1.270458 -5.609147

H 2.109988 0.771470 0.047045 H 0.673918 1.461082 -4.959295

H 0.525009 0.716047 0.799083 H 0.911347 0.783717 -6.577151

H 1.885471 -3.192470 2.189827 H -2.960058 -2.110952 1.262768

H 0.154067 -3.117058 2.405619 H -1.304150 -1.512614 1.805622

H 1.465698 -0.639927 -2.295194 H -1.689970 0.619932 0.604453

H -2.409719 -4.493266 0.469549 H -3.343407 0.016677 0.079031

H -4.283563 -2.926157 -0.672236

H 0.118175 8.057493 -8.769325 ! Chain Shuttle Ethylene Insertion -

H 2.188967 9.316482 -9.329246 Product !

H 2.043709 9.100095 -7.578756 scf done: -1807.872236

H 3.169146 8.095382 -8.501676 C 3.699659 ■0.767596 4.890617

H 1.286042 7.548236 -10.919230 C 3.584243 ■1.919272 3.933360

H 2.201478 6.262202 -10.121179 C 3.501141 ■3.274001 4.369640

H 0.445710 6.123230 -10.305164 C 3.527460 ■3.672777 5.819854

H -1.611395 -0.540010 -2.745052 C 3.429166 ■2.459949 6.758558

H -0.617625 0.505919 -1.678304 C 4.231933 ■1.262335 6.243429

H 1.594874 -5.414981 -0.270776 C 3.711203 ■1.926990 2.520255

H 0.192759 -5.033288 0.713682 C 3.738281 ■3.281176 2.081710

H -0.606518 -6.449702 -1.099998 C 3.611352 ■4.123012 3.225180

H 0.263549 -5.521233 -2.306611 Zr 1.433759 ■2.993313 2.788881

H 1.156062 -3.275768 -2.707888 C 0.398969 ■2.098562 4.606313

H -2.604952 1.879587 -1.131670 C -0.640070 -1.148131 3.981165

H -2.124833 1.950077 -2.802818 C 3.614186 ■5.628409 3.214128

H -3.972242 0.497241 -3.492537 C 2.660735 ■6.152868 2.132116

H -4.439544 0.200076 -1.823737 C 1.345060 ■5.426933 2.207664

H -4.928588 2.642413 -1.527967 C 0.653291 ■4.788616 1.142095

H -4.459567 2.940990 -3.193360 C -0.551647 -4.215590 1.663458

H -6.317075 1.452321 -3.990959 C -0.592712 -4.485530 3.052834

H -6.770816 1.123399 -2.325338 C 0.578937 ■5.210044 3.394302

H -7.224704 3.569521 -1.976881 C 1.002271 ■4.743790 -0.324961

H -6.818271 3.888447 -3.660759 C -0.248561 -4.471882 -1.171301

H -9.172669 2.104566 -2.743022 C -1.063518 -3.299571 -0.620046

H -10.322158 3.088277 -4.645398 C -1.607975 -3.605872 0.780822

H -8.817109 4.075902 -5.077356 C -0.031484 -0.158558 2.971171

H -2.986524 3.883627 -9.109617 C -0.963410 0.978188 2.535577

H -3.462591 4.117570 -7.442017 C -2.238972 0.545795 1.812678

H -5.064850 5.913766 -8.150150 C -3.129035 1.726055 1.418284

H -4.581781 5.682643 -9.820989 C -4.424528 1.302654 0.726209

H -5.389571 3.303360 -9.727380 C -5.327602 2.488467 0.357848

H -5.876625 3.534253 -8.056045 C -6.628505 2.062905 -0.255719

H -7.490365 5.324574 -8.774043 C -7.049767 2.395138 -1.476021

H -6.993818 5.099572 -10.442575 Al 1.419594 4.779940 -4.165881

H -7.769408 2.714354 -10.346311 C 1.371426 3.104639 -3.075695 C 2.720089 2.548697 -2.601514 H 2.508581 -7.232999 2.245924

C 2.601073 1.290270 -1.739848 H 3.101366 -6.005092 1.141021

C -0.252872 5.443517 -5.020838 H 3.888506 -3.617251 1.061920

C -1.457399 4.492725 -5.055639 H -1.233122 1.546901 3.436409

C -2.705412 5.100187 -5.704110 H -0.403570 1.671942 1.894950

C -3.907808 4.155384 -5.738874 H -1.973434 -0.022520 0.908725

C -5.149413 4.771866 -6.384808 H -2.818176 -0.134739 2.450552

C -6.353819 3.819415 -6.414689 H -3.373322 2.308060 2.318095

C -7.558397 4.418346 -7.078248 H -2.566021 2.403709 0.761179

C -8.739350 4.622751 -6.493951 H -4.192113 0.733325 -0.184104

C 3.093584 5.855979 -4.294645 H -4.979603 0.617505 1.382470

C 3.317252 6.616357 -5.614881 H -5.532540 3.067301 1.270896

C 3.414888 5.651328 -6.799394 H -4.797489 3.162057 -0.327275

C 4.559471 7.510820 -5.551804 H -7.261392 1.425324 0.365065

H -1.896679 -3.067067 -1.290965 H -8.005917 2.052441 -1.863581

H 3.782616 -2.750623 7.753427 H -6.455815 3.030193 -2.131230

H 2.379444 -2.165773 6.876174 H -1.191599 3.572742 -5.596642

H 1.468210 -5.688807 -0.624605 H -1.709981 4.170503 -4.034774

H -2.052107 -2.713920 1.237131 H -2.977821 6.018576 -5.164338

H 3.076166 6.576412 -3.458971 H -2.459112 5.414978 -6.728369

H 3.965009 5.214623 -4.090981 H -3.635448 3.238016 -6.280921

H -0.013763 5.775590 -6.042867 H -4.151730 3.839957 -4.713764

H -0.533917 6.373339 -4.497250 H -5.429984 5.686496 -5.845690

H 0.827390 2.333669 -3.644435 H -4.909444 5.084387 -7.410702

H 0.726602 3.303155 -2.202366 H -6.063197 2.904265 -6.952475

H -0.878343 -5.370922 -1.184429 H -6.610246 3.512788 -5.392469

H 0.046647 -4.277888 -2.207513 H -7.429018 4.713167 -8.121674

H -0.432416 -2.398121 -0.594127 H -9.572707 5.069188 -7.030824

H -2.426471 -4.333817 0.694159 H -8.918887 4.349420 -5.455298

H 1.751103 -3.963829 -0.531563 H 3.355166 2.323069 -3.468831

H 4.197090 -0.444924 6.971265 H 3.261978 3.316875 -2.033537

H 5.287394 -1.545403 6.135862 H 3.584425 0.921590 -1.421054

H 4.365604 -0.007360 4.467419 H 2.008154 1.490316 -0.838006

H 2.730133 -0.274429 5.044019 H 2.102935 0.483034 -2.291313

H 4.477692 -4.195669 5.998448 H -0.085751 -2.811797 5.280985

H 2.740171 -4.399249 6.053525 H 1.089343 -1.507900 5.216454

H 3.834826 -1.052122 1.889925 H -1.127178 -0.554871 4.770244

H 0.826285 -5.574837 4.384324 H -1.450168 -1.713831 3.503308

H -1.384696 -4.203894 3.734362

H 2.448272 7.268708 -5.788684 ! Internal Cyclisation - Adduct !

H 4.701400 8.074435 -6.482088 scf done: -1137.146514

H 4.489269 8.235650 -4.732761 Zr 0.024050 -0.155483 0.085860

H 5.464027 6.911920 -5.385715 C -1.178559 1.236794 2.127397

H 3.566806 6.182977 -7.745717 C -1.244889 2.412716 1.467035

H 4.255018 4.956501 -6.672593 C -0.378597 1.068405 -1.820995

H 2.502778 5.049135 -6.912263 C 0.085359 2.463250 -2.272377

H 0.314802 -0.681671 2.046421 C -0.292842 3.690224 -1.432719

H 0.868656 0.287804 3.414554 C -1.783686 4.045563 -1.319957

H 4.629632 -6.009475 3.051146 C -2.725989 3.143421 -0.513048

H 3.300756 -5.996769 4.196441 C -2.506175 3.072460 1.013090 C 2.093682 -0.348181 1.698945 H -1.860340 5.061484 -0.908290

C 2.232555 0.939755 1.089930 H -2.190753 4.112955 -2.338275

C 2.452343 2.188428 1.903736 H -0.321309 2.957297 1.288134

C 3.068413 1.816091 3.259854 H -3.744330 3.525986 -0.652793

C 2.223082 0.760625 3.975204 H -2.734243 2.125642 -0.915043

C 2.147957 -0.561178 3.190151 H -2.498152 4.097213 1.411160

C 2.163753 -1.335097 0.679413 H -3.361356 2.559198 1.467027

C 2.307291 -0.649279 -0.565846 H -0.238817 0.890592 2.564835

C 2.357235 0.749296 -0.307686 H -2.078881 0.694336 2.405302

C 2.086587 -2.824087 0.870525

C 1.106252 -3.444881 -0.132623 ! Internal Cyclisation - Transition State !

C -0.172743 -2.652150 -0.190043 scf done: -1136.934976

C -0.834604 -2.193958 -1.370446 Zr -0.729234 -1.027579 -1.792486

C -2.025685 -1.513988 -0.986733 C -1.770405 0.329369 -0.137205

C -2.096880 -1.533998 0.430597 C -1.930386 1.317949 -1.128363

C -0.963120 -2.242466 0.922021 C -1.429710 0.638874 -3.284597

C -3.086510 -1.100556 -1.968822 C -0.904725 1.889687 -4.006958

C -2.635488 -1.277348 -3.427577 C -1.088794 3.268731 -3.353842

C -1.808870 -2.548773 -3.630697 C -2.534876 3.736937 -3.111181

C -0.514238 -2.510692 -2.806364 C -3.559200 2.663515 -2.729764

H -3.518225 -1.292723 -4.075162 C -3.303054 1.861200 -1.449261

H 2.630269 0.557309 4.970793 C 1.346759 -1.160172 -0.210070

H 1.215682 1.166645 4.139785 C 1.473039 0.120583 -0.823654

H 0.004911 -3.473416 -2.866776 C 1.630535 1.385461 -0.025569

H -3.420438 -0.070020 -1.794839 C 2.196999 1.054618 1.363093

H -2.398559 -3.428130 -3.339061 C 1.371732 -0.031806 2.055998

H -1.562996 -2.671322 -4.690739 C 1.384630 -1.361333 1.282760

H -2.035869 -0.413032 -3.736391 C 1.426970 -2.160027 -1.226907

H -3.965224 -1.732767 -1.779970 C 1.588350 -1.483207 -2.471911

H 0.165739 -1.766009 -3.242158 C 1.601124 -0.080936 -2.220740

H 3.155399 2.713108 3.881765 C 1.358453 -3.650569 -1.019799

H 4.086390 1.435136 3.106394 C 0.344167 -4.301029 -1.973061

H 3.105244 2.873265 1.352052 C -0.949826 -3.529928 -1.994554

H 1.520499 2.737486 2.087929 C -1.634446 -3.051715 -3.150019

H 3.051174 -1.150544 3.398302 C -2.807680 -2.351722 -2.725250

H 1.311845 -1.171600 3.554061 C -2.843940 -2.396538 -1.309541

H 2.520373 1.524900 -1.043541 C -1.706632 -3.118123 -0.856388

H -0.756002 -2.468068 1.962599 C -3.871023 -1.888137 -3.683026

H -2.913112 -1.146130 1.028772 C -3.397831 -1.953478 -5.142041

H -1.464059 0.992265 -1.967846 C -2.624372 -3.240841 -5.432675

H 0.030354 0.347594 -2.552576 C -1.334380 -3.320553 -4.603735

H 3.080804 -3.275263 0.761374 H -4.264829 -1.873594 -5.805910

H 1.762814 -3.039744 1.893997 H 1.750575 -0.206755 3.068262

H 0.900260 -4.488784 0.133131 H 0.341037 0.325726 2.178238

H 1.560537 -3.463905 -1.128291 H -0.873966 -4.308955 -4.709233

H 2.423858 -1.116550 -1.537168 H -4.228819 -0.880695 -3.437479

H 1.178239 2.467580 -2.375441 H -3.256613 -4.108320 -5.202304

H -0.293106 2.641176 -3.291892 H -2.378645 -3.302919 -6.497971

H 0.195956 4.555510 -1.900012 H -2.754467 -1.092234 -5.367424

H 0.164554 3.614489 -0.439579 H -4.741014 -2.547612 -3.557738 H -0.605482 -2.602567 -5.005242 C 2.365412 0.740615 -0.209902

H 2.217146 1.960857 1.977395 C 2.579983 -2.905308 0.731548

H 3.236953 0.717918 1.260649 C 1.612739 -3.615700 -0.231793

H 2.292169 2.076319 -0.559603 C 0.236242 -3.010916 -0.140197

H 0.673962 1.912770 0.098253 C -0.641648 -2.669159 -1.207841

H 2.312431 -1.902452 1.515419 C -1.824174 -2.083328 -0.652599

H 0.570573 -2.008335 1.631182 C -1.681313 -2.066005 0.756485

H 1.755316 0.694969 -2.960297 C -0.419160 -2.631993 1.074041

H -1.471103 -3.342826 0.178104 C -3.018499 -1.705482 -1.483225

H -3.630772 -1.996718 -0.682421 C -2.676674 -1.668340 -2.977862

H -2.471303 0.441870 -3.540509 C -1.839846 -2.880236 -3.393266

H -0.868288 -0.221436 -3.768180 C -0.475165 -2.902516 -2.688205

H 2.348903 -4.102227 -1.156912 H -3.601930 -1.628059 -3.561280

H 1.072223 -3.852430 0.017595 H 1.797909 0.262411 5.034284

H 0.166469 -5.342583 -1.678230 H 0.518214 0.610075 3.880073

H 0.756645 -4.334245 -2.986611 H 0.026196 -3.862092 -2.856438

H 1.719376 -1.955249 -3.439262 H -3.447577 -0.752641 -1.152040

H 0.168431 1.764914 -4.188914 H -2.387364 -3.798720 -3.143748

H -1.372238 1.918274 -5.002614 H -1.690234 -2.887319 -4.477592

H -0.602108 3.996926 -4.013771 H -2.124535 -0.747192 -3.215142

H -0.509126 3.311773 -2.425521 H -3.799363 -2.459340 -1.310821

H -2.523891 4.525999 -2.348174 H 0.179534 -2.143076 -3.144520

H -2.907108 4.215793 -4.024959 H 2.116325 2.542344 4.147100

H -1.112884 2.021920 -1.222519 H 3.426282 1.519923 3.566920

H -4.531623 3.154450 -2.602813 H 2.632492 2.821502 1.658084

H -3.697035 1.985241 -3.578061 H 0.956699 2.459632 2.031599

H -3.498952 2.520492 -0.588296 H 3.004890 -1.127379 3.494760

H -4.042345 1.055184 -1.364808 H 1.333984 -1.634371 3.388784

H -0.961967 0.465431 0.576256 H 2.472461 1.580282 -0.888096

H -2.663573 -0.139266 0.266930 H -0.036638 -2.796016 2.074214

H -2.414753 -1.711107 1.469043

! Internal Cyclisation - Product ! H -2.323424 1.501193 -1.490407 scf done: -1137.176917 H -0.645221 1.034778 -1.642838

Zr 0.184997 -0.536983 -0.033284 H 3.611785 -3.207143 0.517015

C -1.132971 1.039417 0.978642 H 2.378111 -3.217438 1.760997

C -1.059268 2.294060 0.079665 H 1.576697 -4.689193 -0.006393

C -1.307172 1.902912 -1.389154 H 1.981414 -3.529928 -1.259384

C -1.038921 2.972488 -2.482484 H 2.890140 -1.003526 -1.513881

C -0.297343 4.223764 -2.000048 H -0.464539 2.514862 -3.296626

C -1.147880 5.172778 -1.123398 H -1.991217 3.270857 -2.934908

C -2.337459 4.521070 -0.412199 H 0.057183 4.772891 -2.879895

C -2.011749 3.399660 0.580582 H 0.610330 3.922867 -1.462604

C 2.090771 -0.509993 1.694191 H -0.500688 5.668340 -0.388778

C 2.071928 0.821866 1.175774 H -1.546846 5.974665 -1.756402

C 1.970524 2.040909 2.049567 H -0.039672 2.697333 0.132378

C 2.343980 1.691695 3.496587 H -2.894406 5.300549 0.122498

C 1.599631 0.442896 3.972795 H -3.035517 4.138393 -1.167744

C 2.007558 -0.798886 3.169200 H -1.573355 3.826290 1.492778

C 2.443457 -1.407828 0.636450 H -2.956400 2.933614 0.891924

C 2.610413 -0.624965 -0.535673 H -0.849221 1.282452 2.010749 H -2.177262 0.700619 1.021875 H 3.578927 -0.651907 3.423199

H 2.048781 -1.423805 3.735074

! After Cyclisation Ethylene Insertion - H 1.874862 1.809977 -0.706283 Adduct ! H -0.292234 -3.460883 1.631662 scf done: -1215.729461 H -2.617932 -2.460482 0.673468

C 2.492546 -0.494936 3.358325 H -3.140628 0.988358 -1.415021

C 2.183362 -0.251347 1.905143 H -2.316711 1.672349 -2.796255

C 1.901003 1.054129 1.391516 H 3.796670 -2.776114 0.798561

C 1.751443 2.258985 2.279154 H 2.408453 -2.995926 1.847972

C 2.491355 2.035149 3.605833 H 2.040852 -4.441949 -0.065074

C 2.113976 0.697246 4.248640 H 2.487795 -3.185353 -1.202013

C 1.988895 0.981996 -0.018646 H 2.466772 -0.711500 -1.394952

C 2.286731 -0.358257 -0.387243 H -4.381651 2.871557 -1.999183 C 2.405613 -1.132376 0.806972 H -3.547207 3.318114 -0.533161

Zr -0.010587 -0.559055 0.429917 H -2.711504 5.187206 -1.590979

C -1.416139 1.300449 0.506426 H -3.609623 4.739992 -3.018159

C -1.221792 1.851157 -0.914604 H -1.666574 3.361427 -3.810867

C -2.533898 1.841728 -1.736588 H -1.364014 5.073770 -3.711415

C -3.389172 3.108699 -1.598619 H -0.500642 1.186586 -1.471526

C -2.848022 4.377431 -2.318555 H 0.450652 3.381248 -2.778192

C -1.542541 4.183863 -3.096581 H 0.156988 4.908309 -1.975368

C -0.304994 3.940497 -2.209298 H 0.347200 3.203639 -0.293156

C -0.581570 3.250060 -0.871497 H -1.252587 3.883921 -0.277720

C 2.715025 -2.603627 0.872004 H -1.128375 2.036416 1.264374

C 1.983621 -3.362689 -0.247393 H -2.467907 1.047803 0.681877 C 0.545802 -2.931216 -0.361696 H -1.650564 -2.127032 3.027299 C -0.069082 -2.319515 -1.493424 H -0.004724 -1.506616 3.593540 C -1.452189 -2.087532 -1.183337 H -0.802307 0.837009 3.258842 C -1.667456 -2.478162 0.153214 H -2.433298 0.183595 2.697345

C -0.433244 -2.995752 0.663674

C -2.470222 -1.762481 -2.241426 ! After Cylcisation Ethylene Insertion - C -1.816806 -1.339990 -3.562348 Transiton State ! C -0.645924 -2.253378 -3.926078 scf done: -1215.503701 C 0.481574 -2.150829 -2.889998 C 2.381031 -0.827645 3.787978 C -0.983422 -1.284672 3.179633 C 2.208549 -0.437125 2.346083

C -1.411612 -0.022380 2.997390 C 2.046210 0.914687 1.929457

H -2.570664 -1.351269 -4.356462 C 1.938087 2.054119 2.905299 H 2.614820 0.590967 5.216643 C 2.576855 1.664059 4.246511

H 1.037260 0.686748 4.460311 C 2.042020 0.321982 4.749107

H 1.244612 -2.912374 -3.084242 C 2.188956 0.948256 0.519691 H -3.195715 -1.018874 -1.900057 C 2.452727 -0.368415 0.063575 H -0.995917 -3.292461 -3.984725 C 2.450121 -1.239196 1.193882 H -0.254133 -1.995542 -4.915536 Zr 0.084984 -0.516810 0.720573 H -1.456485 -0.305277 -3.490328 C -1.061488 1.670606 0.971114 H -3.045218 -2.683926 -2.412106 C -1.135084 1.729555 -0.551551 H 0.984486 -1.181910 -3.012332 C -2.593556 1.607892 -1.035706 H 2.268049 2.858199 4.292590 C -3.409281 2.908165 -0.983258

H 3.574081 2.058874 3.425894 C -3.010668 4.008019 -2.005599

H 2.140678 3.146660 1.769444 C -2.020135 3.560233 -3.083741

H 0.692847 2.468797 2.484633 C -0.583520 3.320364 -2.564267 C -0.450949 3.014524 -1.067944 H -0.867878 3.850968 -0.494098

C 2.718269 -2.717998 1.166934 H -0.226082 2.250122 1.367947

C 2.031706 -3.355375 -0.046980 H -1.978555 2.093083 1.374251

C 0.617631 -2.860730 -0.180585 H -1.501440 -1.780250 2.839529

C 0.050410 -2.198572 -1.308833 H -0.067042 -0.956901 3.619663

C -1.335439 -1.964646 -1.033733 H -1.159345 1.221320 3.255060

C -1.599376 -2.394200 0.283152 H -2.565588 0.363820 2.459538

C -0.392373 -2.947944 0.814397

C -2.317649 -1.624196 -2.120742 ! After Cyclisation of Ethylene Insertion

C -1.622042 -1.138848 -3.396789 - Product !

C -0.433486 -2.030886 -3.757191 scf done: -1215.776982

C 0.653986 -1.977415 -2.675598 C 2.439529 -0.921878 3.328636

C -0.888291 -0.890635 2.917143 C 2.401181 -0.510819 1.881061

C -1.512012 0.345420 2.718974 C 2.206253 0.837721 1.461348

H -2.345858 -1.118007 -4.218285 C 2.024533 1.968881 2.434183

H 2.456040 0.094142 5.736812 C 2.569972 1.570575 3.813589

H 0.955042 0.400836 4.885911 C 2.014760 0.218266 4.265980

H 1.418712 -2.736151 -2.873611 C 2.419681 0.887308 0.057553

H -3.080966 -0.918784 -1.784148 C 2.779786 -0.416926 -0.383570

H -0.779428 -3.066122 -3.876578 C 2.765646 -1.293035 0.739252

H -0.006481 -1.727947 -4.718937 Zr 0.405292 -0.688907 0.236956

H -1.268547 -0.106992 -3.264870 C -2.132034 2.071456 0.955438

H -2.855531 -2.555606 -2.350063 C -1.568366 2.259841 -0.464261

H 1.167502 -1.007951 -2.737812 C -2.635677 2.037374 -1.550976

H 2.383536 2.448030 4.986300 C -3.611026 3.200131 -1.789315

H 3.666338 1.603549 4.126531 C -2.990821 4.511211 -2.333352

H 2.421452 2.945930 2.491302 C -1.619638 4.342057 -2.993008

H 0.888056 2.331036 3.079969 C -0.459510 4.065000 -2.000579

H 3.437023 -1.101633 3.922523 C -0.869674 3.621053 -0.592585

H 1.813135 -1.731421 4.042164 C 3.096309 -2.762301 0.711334

H 2.169149 1.837564 -0.097538 C 2.319428 -3.468577 -0.409638

H -0.284760 -3.433855 1.776190 C 0.866868 -3.075397 -0.366951

H -2.567269 -2.385669 0.770767 C 0.069266 -2.598508 -1.444640

H -3.105429 0.854656 -0.424066 C -1.246339 -2.325439 -0.948738

H -2.611187 1.228629 -2.060191 C -1.252190 -2.608030 0.440329

H 3.797913 -2.915631 1.144484 C 0.041877 -3.067875 0.800346

H 2.342259 -3.171462 2.090176 C -2.400450 -1.972559 -1.846242

H 2.043414 -4.448112 0.039473 C -1.923428 -1.566488 -3.245623

H 2.587292 -3.111702 -0.957502 C -0.845792 -2.517192 -3.770984

H 2.668416 -0.652537 -0.959167 C 0.422371 -2.470364 -2.906770

H -4.452844 2.622860 -1.159478 C -0.917953 0.023439 1.949916

H -3.388319 3.319505 0.033667 C -2.253813 0.626059 1.454391

H -2.594759 4.876015 -1.480116 H -2.777916 -1.544432 -3.929410

H -3.917589 4.375382 -2.498412 H 2.356365 -0.009942 5.280960

H -2.404050 2.660183 -3.577989 H 0.920623 0.274652 4.311177

H -1.984172 4.325079 -3.867720 H 1.110376 -3.273104 -3.193597

H -0.565527 0.878003 -1.035027 H -3.035091 -1.196243 -1.403729

H -0.099037 2.531247 -3.154196 H -1.239875 -3.541631 -3.778869

H 0.010081 4.225544 -2.742283 H -0.591445 -2.269208 -4.806524

H 0.611765 2.985652 -0.808596 H -1.522685 -0.541799 -3.226203 H -3.037935 -2.863766 -1.929983 C 4.817705 -3.800361 -5.545672

H 0.959364 -1.531607 -3.112199 C 3.832456 -3.169421 -6.542253

H 2.316172 2.345903 4.543899 C 2.676712 -2.523636 -5.823725

H 3.666232 1.522269 3.771760 C 2.231363 -1.170897 -5.949511

H 2.541597 2.858599 2.057324 C 1.089189 -0.990737 -5.114864

H 0.966765 2.246407 2.532883 C 0.844702 -2.216539 -4.448360

H 3.474130 -1.214017 3.557895 C 1.820312 -3.160052 -4.882618

H 1.831326 -1.814782 3.515630 C 0.219439 0.234265 -5.161525

H 2.385439 1.779499 -0.558656 C 0.830767 1.353999 -6.016969

H 0.343982 -3.390881 1.790300 C 1.516735 0.811961 -7.272432

H -2.103767 -2.525932 1.103216 C 2.691445 -0.110119 -6.915114

H -3.223234 1.145666 -1.296296 C 1.830368 -1.061588 -0.627270

H -2.138459 1.805809 -2.500300 C 0.547216 -0.302226 -0.582160

H 4.175041 -2.910483 0.579802 C 0.052778 -0.107941 0.865560

H 2.840753 -3.206104 1.678735 C -1.274929 0.648579 0.922476

H 2.425068 -4.556588 -0.319937 C -1.812739 0.832980 2.342405

H 2.740098 -3.196168 -1.382921 C -3.169245 1.544655 2.386500

H 3.048075 -0.692861 -1.397610 C -3.740630 1.722589 3.798697

H -4.355370 2.835417 -2.507488 Al -5.544983 2.570036 3.946485

H -4.172043 3.410881 -0.870600 C -6.254975 2.959065 5.769430

H -2.911017 5.254734 -1.531358 C -5.308389 2.678526 6.945425

H -3.681469 4.948204 -3.063406 C -5.916110 2.987849 8.317238

H -1.678830 3.544259 -3.743438 C -4.980368 2.680612 9.487372

H -1.387530 5.251869 -3.557928 C -5.584059 3.003264 10.854622

H -0.781937 1.480353 -0.642252 C -4.643251 2.675811 12.023273

H 0.231732 3.329420 -2.435888 C -5.259159 2.943275 13.364451

H 0.129543 4.982208 -1.882426 C 1.976678 -2.319261 -1.099641

H 0.017620 3.623108 0.053462 C -6.515505 2.865748 2.223598

H -1.536466 4.377338 -0.159541 C -7.791619 3.720415 2.157807

H -1.514170 2.630883 1.670494 C -8.926262 3.119819 2.989288

H -3.119269 2.550147 0.983179 C -7.521734 5.169579 2.566996

H -1.121674 -0.814349 2.629607 H 2.695406 -0.564477 -0.184611

H -0.409353 0.779914 2.557821 H 0.697131 0.687711 -1.032789

H -2.973479 0.615475 2.285548 H -0.220923 -0.822937 -1.165537

H -2.725369 0.007381 0.674503 H 0.814578 0.432602 1.442584

H -0.061161 -1.090644 1.340944

! First Vinyl Coordinaiton/Insertion - H -1.152655 1.631731 0.446333 Adduct ! H -2.021093 0.109306 0.321581 scf done: -1650.678150 H 3.096646 -0.578947 -7.818416

C 5.142590 -4.476718 -2.359515 H 0.042624 2.062093 -6.293676

C 5.152259 -3.127542 -3.030106 H -0.742954 -0.069393 -5.596594

C 5.432462 -1.911171 -2.330020 H 1.877942 1.640462 -7.890779

C 5.729202 -1.884864 -0.853253 H 1.562946 1.916824 -5.426529

C 6.249582 -3.258537 -0.408106 H -0.014171 0.602171 -4.155265

C 5.298140 -4.379614 -0.831663 H 5.804262 0.156683 -3.082025

C 5.560338 -0.877311 -3.287981 H 4.838226 -1.630192 -0.262295

C 5.348093 -1.442607 -4.573115 H 7.239916 -3.429742 -0.849879

C 5.107335 -2.842336 -4.422644 H 5.653988 -5.342314 -0.450635

Zr 3.145004 -1.562729 -3.554095 H 4.248513 -5.060116 -2.614860

C 3.053300 0.701559 -3.310014 H 5.987611 -5.046579 -2.769445 H 4.321275 -4.213945 -0.357251 ! First Vinyl Coordinaiton/Insertion -

H 6.381746 -3.269262 0.678781 Transition State !

H 6.466547 -1.103126 -0.641551 scf done: -1650.615896

H 0.020178 -2.420079 -3.775341 C -1.652683 ■2.182971 0.227180

H 5.400708 -0.907857 -5.514001 C -1.310505 ■0.883055 -0.454581

H 0.791659 0.255221 -7.880994 C -0.936164 0.293156 0.260053

H 3.503024 0.492844 -6.487180 C -0.865628 0.335650 1.761485

H 1.873658 -4.202142 -4.585232 C -0.666574 ■1.084729 2.310061

H 4.395747 -4.724729 -5.137061 C -1.720489 ■2.047336 I.758638

H 5.745054 -4.086241 -6.057976 C -0.487584 1.249389 -0.684661

H 3.467030 -3.928609 -7.243951 C -0.556745 0.661544 -1.979254

H 4.346386 -2.415060 -7.146145 C -1.068722 ■0.662912 -1.845142

H 2.016241 1.057859 -3.274727 Zr -2.932488 0.936452 -1.381345

H 3.534374 0.979221 -2.360182 C -3.146290 3.186820 -0.771350

H 3.568687 1.269729 -4.093581 C -1.314993 ■1.636923 -2.968592

H 1.118978 -2.883889 -1.460699 C -2.098610 ■0.975723 -4.114214

H 2.909244 -2.863471 -0.956086 C -3.277213 ■0.197333 -3.587676

H -1.907489 -0.148916 2.828000 C -3.595851 1.165853 -3.857021

H -1.085932 1.399439 2.941758 C -4.779965 1.509041 -3.130850

H -3.068056 2.524626 1.897879 C -5.189377 0.357532 -2.412803

H -3.878987 0.980055 I.764651 C -4.268026 ■0.687173 -2.683632

H -3.799783 0.740469 4.297510 C -5.512694 2.807396 -3.334511

H -3.034108 2.296001 4.419463 C -4.669071 3.827081 -4.112436

H -7.181422 2.375982 5.898824 C -3.940868 3.180146 -5.292417

H -6.589490 4.007658 5.805076 C -2.936117 2.118978 -4.822924

H -4.994289 1.624818 6.928389 C -4.076357 2.020716 0.830610

H -4.383485 3.262128 6.831143 C -5.316298 2.874118 0.951146

H -6.207766 4.047562 8.349693 C -5.962481 2.653655 2.330453

H -6.847722 2.415504 8.434716 C -7.257482 3.449029 2.510356

H -4.699266 1.617665 9.458035 C -7.881208 3.265260 3.894912

H -4.044217 3.244028 9.362541 C -9.215228 3.997701 4.076769

H -5.853109 4.067138 10.898421 C -9.816195 3.843805 5.479722

H -6.523408 2.446357 10.979366 Al -11.609306 4.657602 5.822656

H -4.365562 1.612638 I I.959811 C -12.156282 4.922369 7.722842

H -3.712135 3.248188 11.923028 C -11.044782 4.815554 8.777130

H -6.734014 1.856713 1.832855 C -11.538461 5.022865 10.212323

H -5.770454 3.266956 1.517614 C -10.438933 4.907923 I I.268937

H -8.135166 3.740323 1.110893 C -10.938072 5.150260 12.693802

H -9.854982 3.690235 2.870581 C -9.833604 5.022391 13.752747

H -9.135568 2.084978 2.693087 C -10.334452 5.234275 15.150614

H -8.678441 3.117014 4.058082 C -4.188846 0.627605 0.589263

H -8.417896 5.791852 2.460206 C -12.731576 5.043525 4.213089

H -7.203579 5.232867 3.616048 C -14.111260 5.709385 4.348465

H -6.732928 5.619726 1.952618 C -15.077008 4.853290 5.169709

C -4.792000 3.801596 14.271606 C -14.002285 7.123181 4.922560

H -6.170063 2.384356 13.589174 H -3.256634 2.327673 1.477433

H -5.291323 3.952247 15.225638 H -5.082030 3.937523 0.840968

H -3.889721 4.384922 14.095165 H -6.031914 2.606663 0.164423

H -5.246062 2.937881 3.113442

H -6.166778 1.584932 2.471902 H -7.061090 4.516476 2.337397 H -12.102065 5.641885 3.534160

H -7.979283 3.141841 1.740016 H -14.545326 5.805878 3.340304

H -2.541166 1.562087 -5.679628 H -16.076214 5.302174 5.212891

H -5.317498 4.635735 -4.465420 H -15.185602 3.850166 4.740430

H -6.424733 2.585925 -3.905988 H -14.726139 4.736633 6.202898

H -3.418396 3.942476 -5.879737 H -14.979593 7.618403 4.962598

H -3.930932 4.291001 -3.444530 H -13.601834 7.107766 5.944385

H -5.854775 3.232468 -2.383446 H -13.340043 7.750869 4.314423

H -0.104471 2.237326 -0.456043 C -9.911492 6.183048 15.986535

H -1.777301 0.763955 2.200880 H -11.116961 4.549609 15.484473

H 0.336081 -1.440355 2.039241 H -10.321464 6.286260 16.988259

H -1.598336 -3.038646 2.207510 H -9.135737 6.891879 15.701422

H -2.586513 -2.612743 -0.154959

H -0.866751 -2.904657 -0.034118 ! First Vinyl Coordination/Insertion -

H -2.715578 -1.700046 2.065505 Product !

H -0.710828 -1.066198 3.404126 scf done: -1650.694558

H -0.042931 0.989467 2.070691 C 4.214761 -3.785676 -1.124649

H -6.075690 0.275669 -1.796303 C 4.610179 -2.701939 -2.090437

H -0.239184 1.127758 -2.905296 C 4.774144 -1.338862 -1.702512

H -4.674411 2.712603 -5.962212 C 4.566274 -0.870960 -0.288832

H -2.071400 2.621024 -4.365180 C 4.649475 -2.057048 0.682440

H -4.329327 -1.698913 -2.298126 C 3.759368 -3.215427 0.226072

H -1.875737 -2.494187 -2.581772 C 5.320201 -0.641536 -2.814827

H -0.364438 -2.036640 -3.343482 C 5.516673 -1.574359 -3.873484

H -2.433121 -1.737841 -4.828719 C 5.080201 -2.854825 -3.432511

H -1.441303 -0.300725 -4.671719 Zr 3.057132 -1.399038 -3.718290

H -4.024927 3.757955 -1.069021 C 2.094812 1.385543 -3.434253

H -2.537061 3.770448 -0.080984 C 5.111590 -4.133338 -4.227973

H -2.518392 3.099406 -1.704099 C 4.387248 -3.965246 -5.572268

H -5.179611 0.240325 0.364349 C 3.066479 -3.269424 -5.377646

H -3.573539 -0.030088 1.196053 C 2.565355 -2.161976 -6.114139

H -8.034010 2.193393 4.086968 C 1.296620 -1.785517 -5.563214

H -7.173228 3.611758 4.661287 C 1.012403 -2.669905 -4.490596

H -9.066757 5.063442 3.849483 C 2.101446 -3.571356 -4.364671

H -9.923813 3.631693 3.320152 C 0.416123 -0.737902 -6.189221

H -9.908848 2.769633 5.719167 C 1.195763 0.123747 -7.191023

H -9.108314 4.226447 6.230750 C 2.069997 -0.735630 -8.107448

H -12.942064 4.182019 7.948104 C 3.158239 -1.480398 -7.321958

H -12.665019 5.893275 7.820012 C 1.767465 0.809556 -2.046811

H -10.555295 3.833460 8.706896 C 0.511880 1.528992 -1.516166

H -10.255860 5.552822 8.567828 C 0.091401 1.175125 -0.090622

H -12.014240 6.011381 10.286990 C -1.216232 1.862764 0.309824

H -12.330450 4.291176 10.428425 C -1.696598 1.548189 1.727319

H -9.978613 3.910871 11.209408 C -3.055420 2.181630 2.046783

H -9.637349 5.625140 11.039508 C -3.574761 1.908202 3.464141

H -11.385930 6.150676 12.761996 Al -5.393260 2.612772 3.901008

H -11.744490 4.439702 12.924018 C -6.035254 2.469335 5.784183

H -9.391211 4.017517 13.675667 C -4.965941 2.231620 6.860607

H -9.027635 5.735649 13.537144 C -5.537061 2.116205 8.277634

H -12.842884 4.078107 3.690326 C -4.478736 1.888657 9.358159 C -5.061821 1.806024 10.769642 H 6.770220 1.647015 5.814673

C -3.999009 1.578129 11.854255 H 6.621600 3.365356 6.037162

C -4.583565 1.467961 13.231286 H 4.397997 1.319072 6.628817

C 1.604488 -0.727318 -2.090054 H 4.229251 3.048094 6.844266

C -6.467481 3.304502 2.362112 H 6.102341 3.030430 8.509530

C -7.746274 4.125419 2.597613 H 6.268812 1.295793 8.304164

C -8.829265 3.308442 3.304386 H 3.924724 0.964273 9.138560

C -7.448207 5.420430 3.356274 H 3.738927 2.701303 9.318900

H 2.609098 1.062992 -1.387244 H 5.610883 2.729959 10.995827

H 0.675934 2.614784 -1.580679 H 5.801905 0.994490 10.812266

H -0.321541 1.306843 -2.199895 H 3.452198 0.652190 11.619178

H 0.889773 1.457735 0.610525 H 3.261842 2.390885 11.829404

H -0.031193 0.087983 0.000520 H 6.707625 2.422986 1.742787

H -1.102179 2.951029 0.201443 H 5.771365 3.886762 1.737567

H -2.000374 1.571490 -0.404466 H 8.152389 4.415227 1.615002

H 3.649209 -2.222993 -7.960395 H 9.760676 3.878218 3.405032

H 0.493389 0.717964 -7.784042 H 9.063270 2.391985 2.749725

H -0.396533 -1.255280 -6.717724 H 8.513985 3.015065 4.313372

H 2.537043 -0.116452 -8.879925 H 8.345690 6.039802 3.468743

H 1.831056 0.845659 -6.655550 H 7.068586 5.211009 4.365222

H -0.073176 -0.117265 -5.428990 H 6.694211 6.023739 2.836919

H 5.603990 0.405391 -2.829894 C 4.294985 2.266667 14.259200

H 3.589888 -0.384576 -0.173292 H 5.310989 0.666377 13.375997

H 5.689469 -2.402031 0.754188 H 4.760487 2.135456 15.232996

H 3.765653 -4.016463 0.972772 H 3.578628 3.081464 14.166593

H 3.443407 -4.443310 -1.543296

H 5.096626 -4.423383 -0.969707 ! Second Vinyl Coordination/Insertion -

H 2.721138 -2.866781 0.153469 Adduct !

H 4.356868 -1.727449 1.684826 scf done: -1729.272917

H 5.318662 -0.114464 -0.039511 C 5.162353 -4.046301 -0.045840

H 0.113214 -2.674989 -3.888640 C 5.062812 -3.504065 -1.448661

H 5.956422 -1.355057 -4.840826 C 5.424777 -2.163422 -1.791400

H 1.436920 -1.466308 -8.627320 C 5.919546 -1.178089 -0.764430

H 3.947309 -0.766775 -7.038394 C 6.526211 -1.938082 0.423075

H 2.170101 -4.378432 -3.644176 C 5.543075 -2.966928 0.983901

H 4.634561 -4.927740 -3.645348 C 5.415836 -2.058195 -3.204094

H 6.146782 -4.454407 -4.393793 C 5.028609 -3.317143 -3.734033

H 4.240795 -4.942235 -6.049300 C 4.810662 -4.222826 -2.651154

H 5.007809 -3.377278 -6.256354 Zr 2.980851 -2.512227 -2.686466

H 1.295676 1.184631 -4.157268 C 2.821880 -0.481797 -3.754433

H 2.244074 2.470435 -3.405529 C 3.600700 0.769796 -3.328808

H 3.060485 1.022455 -3.852994 C 3.169665 2.032682 -4.080205

H 0.573957 -0.961760 -2.386072 C 4.358366 -5.651043 -2.796092

H 1.750209 -1.169992 -1.099047 C 3.270822 -5.758885 -3.878726

H -1.768355 0.458637 1.859482 C 2.218428 -4.695595 -3.702064

H -0.951174 1.894574 2.457440 C 1.797238 -3.731112 -4.671549

H -2.982034 3.266479 1.881291 C 0.777136 -2.920438 -4.092171

H -3.785365 1.823109 1.306487 C 0.595516 -3.353269 -2.754121

H -3.597499 0.819766 3.645545 C 1.466736 -4.455095 -2.520974

H -2.856352 2.289806 4.206483 C -0.061695 -1.959748 -4.886429 C 0.489675 -1.738079 -6.302143 H 5.205829 -6.302020 -3.045844

C 1.000980 -3.036510 -6.928850 H 2.813711 -6.755110 -3.854574

C 2.170886 -3.626094 -6.127143 H 3.724699 -5.653064 -4.869041

C 1.917779 -0.618216 -0.314826 H 1.742964 -0.256674 -3.691998

C 0.634287 0.126614 -0.462269 H 3.002629 -0.666200 -4.825582

C 0.327083 0.946378 0.808034 H 1.152089 -2.583712 -0.066830

C -0.956934 1.767500 0.681333 H 2.987681 -2.396401 0.141111

C -1.310156 2.524044 1.963227 H -1.416724 1.806222 2.789023

C -2.593831 3.354227 1.855793 H -0.476889 3.184925 2.241699

C -2.988113 4.053600 3.164622 H -2.470621 4.096659 1.054673

Al -4.631864 5.192205 3.122840 H -3.409609 2.694758 1.524120

C -5.767434 5.275097 4.762315 H -3.088308 3.307891 3.966876

C -5.556640 4.142782 5.778106 H -2.156312 4.701994 3.490872

C -6.464995 4.231848 7.008653 H -6.826563 5.314704 4.466539

C -6.255069 3.093029 8.007893 H -5.584901 6.246218 5.251904

C -7.179104 3.166224 9.224226 H -5.721151 3.169539 5.291989

C -6.968528 2.010549 10.213198 H -4.508933 4.130568 6.111186

C 2.033094 -1.951251 -0.136989 H -6.299181 5.195968 7.510624

C -4.926633 6.209860 1.427682 H -7.514154 4.239824 6.679503

C -6.233652 6.982429 1.186567 H -6.406877 2.130661 7.497249

C -7.439409 6.041722 1.145095 H -5.208771 3.093697 8.346248

C -6.436098 8.093712 2.218041 H -7.027038 4.119016 9.748782

H 2.822769 -0.008576 -0.285778 H -8.225140 3.167930 8.886863

H 0.705733 0.814648 -1.314628 H -7.103753 1.060941 9.673156

H -0.190087 -0.568415 -0.659284 H -5.933648 2.017160 10.578810

H 1.171425 1.613522 1.025920 H -4.769691 5.492513 0.605871

H 0.245249 0.259487 1.660125 H -4.070442 6.901378 1.343949

H -0.853782 2.478296 -0.150540 H -6.169650 7.466594 0.198896

H -1.788720 1.100476 0.413614 H -8.366842 6.582366 0.922825

H 2.438166 -4.614733 -6.516143 H -7.317331 5.268020 0.377587

H -0.295493 -1.300838 -6.927765 H -7.579523 5.534039 2.108549

H -1.070688 -2.390478 -4.953082 H -7.333747 8.684899 2.001560

H 1.320513 -2.857134 -7.960921 H -6.550636 7.683280 3.229187

H 1.306861 -1.007115 -6.272221 H -5.584388 8.784197 2.233403

H -0.181270 -1.002252 -4.365579 H 3.483683 0.954684 -2.251602

H 5.699703 -1.189420 -3.782141 H 4.676112 0.625068 -3.484784

H 5.112211 -0.527362 -0.399648 H 3.744091 2.909320 -3.757746

H 7.444580 -2.443463 0.097201 H 3.317982 1.917636 -5.160242

H 5.968774 -3.457301 1.865421 H 2.108164 2.253550 -3.916745

H 4.246016 -4.564869 0.264869 C -7.915680 2.052355 11.375495

H 5.941908 -4.820225 -0.055273 C -7.562031 2.137532 12.658231

H 4.648051 -2.439768 1.341330 H -8.977756 2.017882 11.123729

H 6.814877 -1.230335 1.207136 H -8.302720 2.166920 13.453634

H 6.660092 -0.512626 -1.220334 H -6.517188 2.176663 12.962100

H -0.143235 -2.969796 -2.060646

H 4.957561 -3.563712 -4.786921 ! Second Vinyl Coordination/Insertion -

H 0.186244 -3.771252 -6.972926 Transition State !

H 3.055883 -2.990423 -6.266492 scf done: -1729.263584

H 1.536304 -5.025909 -1.600851 C -1.824950 -1.583102 0.927149

H 3.967815 -6.011205 -1.838039 C -1.437476 -0.616039 -0.162178 C -0.831212 0.646969 0.101373 H -6.170369 2.557056 -4.451569

C -0.577955 1.140304 1.498593 H -3.051852 2.676713 -6.674997

C -0.452906 -0.057083 2.452632 H -3.372511 3.787602 -4.438852

C -1.661878 -0.987674 2.337611 H -5.438522 3.486713 -3.164342

C -0.410276 1.191487 -1.136399 H 0.116863 2.128403 -1.272494

C -0.738091 0.265595 -2.166682 H -1.392702 1.790626 1.847739

C -1.372944 -0.863547 -1.566934 H 0.465974 -0.611413 2.220217

Zr -2.947044 1.070702 -1.494803 H -1.577095 -1.807013 3.059410

C -2.837124 3.408645 -1.463685 H -2.845584 -1.962026 0.795419

C -1.900205 4.452178 -0.876293 H -1.170140 -2.459850 0.830413

C -1.330471 5.411592 -1.923963 H -2.564788 -0.432090 2.621746

C -1.876108 -2.085538 -2.289227 H -0.354109 0.301386 3.482727

C -2.644785 -1.693253 -3.559762 H 0.332010 1.749655 1.517408

C -3.618058 -0.577356 -3.282317 H -6.186982 0.940555 -1.747105

C -3.664165 0.691436 -3.932362 H -0.497247 0.374252 -3.217975

C -4.737063 1.449893 -3.364272 H -4.525738 1.750989 -6.414146

C -5.328716 0.663045 -2.346578 H -1.914211 1.597549 -4.836573

C -4.645482 -0.580888 -2.292648 H -4.887727 -1.407015 -1.633066

C -5.213997 2.751466 -3.946404 H -2.531473 -2.652193 -1.619466

C -4.216937 3.320505 -4.963298 H -1.042481 -2.753480 -2.541054

C -3.684608 2.233374 -5.899016 H -3.169641 -2.565959 -3.966303

C -2.883734 1.172039 -5.131905 H -1.941354 -1.369769 -4.333273

C -3.901929 2.738765 0.405184 H -3.706195 3.880616 -1.929058

C -5.085406 3.660329 0.237769 H -2.285132 2.926670 -2.333642

C -5.770931 3.900046 1.594581 H -5.107840 0.961751 0.467298

C -6.983839 4.825619 1.480679 H -3.474619 0.836596 1.294347

C -7.660436 5.101348 2.824559 H -7.931372 4.147782 3.300379

C -8.913602 5.976193 2.712702 H -6.942293 5.584041 3.502692

C -9.578670 6.284403 4.059581 H -8.646265 6.914752 2.205962

Al -11.256522 7.371153 4.033090 H -9.630007 5.476970 2.044781

C -12.008410 7.950247 5.787067 H -9.802100 5.341269 4.586302

C -11.464600 7.240944 7.035798 H -8.857742 6.793478 4.719956

C -12.047000 7.775204 8.348015 H -13.104930 7.865403 5.760483

C -11.495661 7.087143 9.597679 H -11.822033 9.034103 5.876324

C -12.081837 7.633661 10.899993 H -11.667332 6.161911 6.971900

C -11.514281 6.954044 12.154557 H -10.369555 7.332220 7.071949

C -4.096012 1.348737 0.566663 H -11.851113 8.855417 8.411049

C -11.999585 7.835782 2.235287 H -13.141169 7.668980 8.324571

C -13.404604 8.446071 2.097853 H -11.692227 6.006747 9.537114

C -14.484258 7.494849 2.617333 H -10.401472 7.194991 9.618726

C -13.501410 9.812991 2.777021 H -11.894743 8.713915 10.963844

H -3.056219 3.170309 0.936787 H -13.174296 7.514326 10.886074

H -4.780331 4.628718 -0.171803 H -11.691680 5.870557 12.076008

H -5.806203 3.219408 -0.461431 H -10.425879 7.091176 12.191158

H -5.044328 4.332078 2.296282 H -11.940702 6.915342 1.631976

H -6.079866 2.938201 2.023007 H -11.261128 8.508190 1.765792

H -6.675716 5.778219 1.026634 H -13.605795 8.604159 1.026022

H -7.713969 4.380719 0.789393 H -15.489835 7.904563 2.465885

H -2.652965 0.324328 -5.786665 H -14.442867 6.525857 2.105787

H -4.701791 4.114749 -5.540214 H -14.366426 7.309313 3.693156 H -14.484685 10.271506 2.618740 C -5.414730 3.729186 5.992254

H -13.349195 9.731192 3.860493 C -5.962276 4.125071 7.367206

H -12.748158 10.507287 2.385992 C -5.548680 3.183341 8.498882

H -2.451488 5.039035 -0.130896 C -6.095426 3.602162 9.864264

H -1.076594 3.966435 -0.339440 C -5.678307 2.658904 11.001816

H -0.680463 6.157129 -1.453831 C 1.439474 -1.231452 -1.843620

H -0.733919 4.882253 -2.676150 C -5.765255 5.188717 1.359609

H -2.127737 5.950174 -2.447952 C -7.100171 5.950684 1.319699

C -12.131379 7.461469 13.424042 C -8.280957 5.029616 1.633228

C -11.472774 8.049899 14.422854 C -7.092767 7.169834 2.243393

H -13.212781 7.335942 13.509525 H 2.673913 0.372457 -1.065852

H -11.984284 8.400193 15.315998 H 1.132591 2.256457 -1.656227

H -10.395099 8.201329 14.387160 H -0.000993 1.101631 -2.339925

H 0.850973 1.235499 0.602470

! Second Vinyl Coordination/Insertion - H -0.303505 0.081837 -0.056527

Product ! H -0.633697 3.124684 -0.152415 scf done: -1729 .299661 H -1.779624 1.960869 -0.791788

C 3.458854 -4.654934 0.097930 H 4.127906 -3.899749 -6.820883

C 4.122486 -3.697189 -0.854684 H 1.098710 -0.901191 -7.511477

C 4.278912 -2.307438 -0.558961 H -0.024797 -2.595741 -6.234156

C 3.787515 -1.684008 0.719716 H 3.215658 -1.963075 -8.197849

C 3.517298 -2.763494 1.777317 H 2.308705 -0.618631 -6.273650

C 2.692396 -3.917009 1.201944 H 0.267209 -1.289782 -5.106602

C 5.093885 -1.753289 -1.579002 H 5.435111 -0.725133 -1.627856

C 5.470787 -2.795708 -2.476518 H 2.867654 -1.112964 0.548685

C 4.877436 -4.007602 -2.031157 H 4.470510 -3.155147 2.156356

Zr 3.055343 -2.501915 -2.844481 H 2.428481 -4.627429 1.992148

C 2.576504 0.605377 -3.195068 H 2.802678 -5.361891 -0.422006

C 3.404702 1.892605 -3.220479 H 4.250570 -5.264419 0.556334

C 4.102115 2.141127 -4.554185 H 1.745484 -3.526474 0.804744

C 4.964615 -5.358360 -2.694948 H 2.999769 -2.313640 2.630876

C 4.444923 -5.320457 -4.143675 H 4.531547 -0.966703 1.083916

C 3.146050 -4.560402 -4.233967 H 0.076711 -3.618929 -3.232879

C 2.804465 -3.546194 -5.173450 H 6.115151 -2.684705 -3.342982

C 1.507184 -3.039039 -4.846822 H 2.029530 -3.220315 -7.865107

C 1.039830 -3.745281 -3.711132 H 4.347977 -2.325323 -6.089344

C 2.043888 -4.676741 -3.330069 H 1.968947 -5.387667 -2.515434

C 0.773769 -2.050862 -5.711770 H 4.376422 -6.073703 -2.111546

C 1.702237 -1.402866 -6.748406 H 5.997336 -5.725410 -2.678216

C 2.631645 -2.430044 -7.398397 H 4.319826 -6.342675 -4.522188

C 3.581071 -3.063276 -6.372593 H 5.187577 -4.842833 -4.791363

C 1.911623 0.240735 -1.848955 H 1.808303 0.641634 -3.980635

C 0.762260 1.227376 -1.557015 H 3.282472 -0.197754 -3.533612

C 0.097609 1.095559 -0.186493 H 0.506259 -1.303696 -2.420424

C -1.031994 2.111193 0.000771 H 1.190297 -1.557188 -0.825286

C -1.727640 2.050128 1.361553 H -2.111964 1.034567 1.536377

C -2.880623 3.052175 1.484675 H -0.994559 2.239039 2.159071

C -3.584820 3.057834 2.847630 H -2.492826 4.057336 1.263380

Al -5.121959 4.321089 3.042709 H -3.609508 2.841016 0.688936

C -5.835872 4.687363 4.868476 H -3.947802 2.043167 3.083452 H -2.855857 3.275584 3.644321 C 3.819475 -5.665375 -3.952807

H -6.933921 4.744692 4.824806 C 4.448692 -4.519940 -3.208794

H -5.522410 5.712395 5.131384 C 4.548733 -4.348202 -1.800969

H -5.746843 2.706841 5.759503 C 5.185713 -3.095342 -1.543518

H -4.318019 3.676102 6.049725 C 5.492846 -2.497825 -2.791027

H -5.628418 5.146030 7.602697 C 5.029605 -3.365237 -3.815110

H -7.059625 4.172551 7.315084 C 5.613287 -2.685013 -0.158146

H -5.889000 2.163163 8.268841 C 5.848378 -3.938963 0.696780

H -4.451234 3.132618 8.547611 C 4.628581 -4.863249 0.684743

H -5.756366 4.619666 10.100606 C 4.275712 -5.368953 -0.726293

H -7.192503 3.650344 9.817948 C 1.452468 -1.288814 -0.243339

H -6.014701 1.640908 10.752801 C 1.741820 -2.606757 -0.283343

H -4.583499 2.618798 11.068997 C 0.110209 -0.673368 -0.452060

H -5.775155 4.398306 0.591754 C -0.395714 0.003896 0.837262

H -4.951075 5.860196 1.036548 C -1.729725 0.724918 0.638719

H -7.248796 6.325495 0.294046 C -2.241071 1.396650 1.914120

H -9.238091 5.558282 1.553173 C -3.560900 2.153242 1.728929

H -8.317573 4.176326 0.945447 C -4.069003 2.826781 3.009684

H -8.212179 4.630785 2.654105 Al -5.736826 3.921972 2.901834

H -8.018672 7.749005 2.147887 C -6.487624 4.260433 1.079709

H -6.998396 6.873755 3.295469 C -7.914450 4.807749 0.905228

H -6.258075 7.841292 2.009892 C -8.071565 6.204653 I.507957

H 2.749245 2.741249 -2.995546 C -6.445886 4.671940 4.608821

H 4.147829 1.860040 -2.412846 C -5.857685 4.093603 5.904171

H 4.676866 3.072238 -4.530535 C -6.428120 4.724987 7.178045

H 4.802648 1.333561 -4.802631 C -5.840508 4.150528 8.467896

H 3.381287 2.222981 -5.375428 C -6.422989 4.776408 9.735673

C -6.251792 3.055086 12.329976 C -5.826568 4.196409 I I.026314

C -5.542521 3.380038 13.411223 C -6.434385 4.779790 12.267232

H -7.341969 3.082326 12.387757 C -5.770764 5.444552 13.213502

H -6.021737 3.665115 14.344594 C -8.956899 3.843393 1.474230

H -4.453706 3.371156 13.404339 H 2.250109 -0.593979 0.024323

H 0.182322 0.093436 -1.235720

! Third Vinyl Coordination/Insertion - H -0.610840 -1.426921 -0.787884 Adduct ! H 0.357703 0.721134 1.189383 scf done: -1807.880730 H -0.494658 -0.754088 1.624831

C 2.812572 -2.130318 -6.477413 H -1.617469 1.479933 -0.152527

C 2.099323 -2.663122 -5.262499 H -2.480696 0.009469 0.275016

C 1.104456 -1.903578 -4.578425 H 3.041612 -2.949201 -7.167934

C 0.617441 -0.564490 -5.056698 H 0.914010 0.778922 -6.719037

C 1.482453 0.005969 -6.190932 H -0.409326 -0.708271 -5.420880

C 1.939503 -1.075019 -7.172308 H 2.500627 -0.622013 -7.996589

C 0.535694 -2.741975 -3.587038 H 2.364431 0.503278 -5.770144

C 1.158674 -4.018859 -3.666181 H 0.544155 0.158644 -4.235857

C 2.122378 -3.982797 -4.710770 H 6.027513 -1.570297 -2.940822

Zr 2.965327 -2.536566 -2.809092 H 4.861879 -2.051181 0.334098

C 3.337497 -0.269725 -3.043688 H 6.724265 -4.477630 0.312510

C 4.230109 0.524569 -2.081839 H 4.805362 -5.727530 1.333426

C 4.056373 2.045280 -2.199358 H 3.240088 -5.731492 -0.751395

C 2.995738 -5.133116 -5.136560 H 4.893994 -6.247246 -0.956341 H 3.775326 -4.332232 1.126219 H -4.696297 5.609462 13.150435

H 6.083653 -3.646022 1.725448 C 4.780160 4.353614 -1.389125

H 6.523525 -2.079567 -0.218466 H 4.788585 2.535974 -0.228408

H -0.279944 -2.474609 -2.924985 H 6.016960 2.589186 -1.482073

H 5.137572 -3.197429 -4.880272 H 5.448001 4.897496 -0.712630

H 1.063867 -1.566671 -7.616509 H 4.988756 4.700639 -2.407716

H 3.775549 -1.675760 -6.207339 H 3.752516 4.647665 -1.145146

H 0.916205 -4.886669 -3.061931

H 3.174546 -6.233728 -3.273755 ! Third Vinyl Coordination/Insertion -

H 4.585732 -6.366368 -4.307556 Transition State !

H 2.383462 -5.936652 -5.562336 scf done: -1807.858695

H 3.668173 -4.803010 -5.934414 C -2.939117 1.119242 -5.153394

H 2.308141 0.126172 -2.979588 C -3.697726 0.650391 -3.935422

H 3.651914 -0.063597 -4.077141 C -4.765823 1.410501 -3.361580

H 0.965561 -3.349376 -0.460776 C -5.259652 2.701007 -3.954143

H 2.710452 -2.967395 0.054919 C -4.287011 3.257683 -5.001306

H -2.368058 0.639174 2.700725 C -3.764267 2.157178 -5.926606

H -1.478944 2.095549 2.287904 C -5.337670 0.634632 -2.324992

H -3.429044 2.903167 0.935610 C -4.645322 -0.603794 -2.262394

H -4.318495 1.453183 I.347968 C -3.634194 -0.609217 -3.268881

H -4.208837 2.069107 3.797336 Zr -2.945191 1.057805 -1.508179

H -3.281534 3.486160 3.413204 C -2.858305 3.393638 -1.483669

H -7.541707 4.572085 4.622962 C -1.919492 4.443873 -0.913966

H -6.272774 5.761007 4.585180 C -1.375650 5.419131 -1.967418

H -6.031062 3.008149 5.942467 C -2.661689 -1.725677 -3.547016

H -4.765082 4.216736 5.906515 C -1.877812 -2.104880 -2.281812

H -6.254798 5.810417 7.149411 C -1.367328 -0.875267 -1.577871

H -7.519919 4.594396 7.184233 C -1.418346 -0.612342 -0.175484

H -6.007682 3.063716 8.491358 C -0.810780 0.654079 0.067763

H -4.749556 4.288750 8.463487 C -0.404325 1.186206 -1.180228

H -6.257549 5.861951 9.721686 C -0.739529 0.247524 -2.196303

H -7.512824 4.634488 9.744413 C -0.544366 1.162566 1.457160

H -5.985160 3.107207 I I.025159 C -0.400964 -0.025195 2.420553

H -4.740453 4.354287 11.037113 C -1.608496 -0.960370 2.331318

H -6.389524 3.314083 0.523996 C -1.790378 -1.569012 0.928620

H -5.772355 4.937493 0.581273 C -3.897057 2.721338 0.394396

H -8.116164 4.898400 -0.174285 C -4.078093 1.329748 0.560905

H -9.977906 4.202661 1.299901 C -5.087905 3.635403 0.238852

H -8.874024 2.849705 1.018090 C -5.753806 3.883408 1.603963

H -8.834617 3.722968 2.559021 C -6.968070 4.808330 1.499241

H -9.069314 6.614572 1.312355 C -7.621838 5.106028 2.849757

H -7.931980 6.188319 2.595842 C -8.870587 5.987748 2.742377

H -7.339815 6.905330 1.088643 C -9.514634 6.325948 4.092460

H 4.042483 0.242060 -1.034003 Al -11.183303 7.426796 4.060488

H 5.286129 0.287641 -2.262154 C -11.938052 7.860152 2.259479

C 4.969771 2.844084 -1.267993 C -13.354909 8.441834 2.119047

H 4.244567 2.345352 -3.240166 C -13.477956 9.813210 2.784772

H 3.008388 2.308908 -1.993884 C -11.911253 8.053163 5.808467

H -7.512219 4.643676 12.377657 C -11.428850 7.304822 7.059965

H -6.274551 5.846846 14.088953 C -11.999802 7.863182 8.367172 C -11.557004 7.098281 9.615440 H -10.330918 7.328291 7.112580

C -12.136806 7.665510 10.911724 H -11.709561 8.919499 8.462831

C -11.708196 6.886044 12.163489 H -13.097791 7.857405 8.308251

C -12.320305 7.423556 13.423015 H -11.851281 6.043024 9.518120

C -11.644820 7.907150 14.465907 H -10.459017 7.101821 9.675954

C -14.414117 7.473888 2.649892 H -11.834530 8.715312 11.023689

H -3.049150 3.159883 0.916635 H -13.234038 7.670483 10.847611

H -4.793621 4.602480 -0.181683 H -12.005184 5.833591 12.038730

H -5.816740 3.186239 -0.446592 H -10.614113 6.893904 12.250824

H -5.017253 4.321272 2.291540 H -11.863038 6.935823 1.664135

H -6.055813 2.924689 2.044134 H -11.213195 8.542314 1.782765

H -6.666974 5.754001 1.026274 H -13.561229 8.584993 1.046080

H -7.710408 4.354727 0.826914 H -15.428111 7.862741 2.499689

H -2.705363 0.263491 -5.796471 H -14.355520 6.501929 2.145756

H -4.789061 4.037631 -5.583035 H -14.288386 7.298566 3.726569

H -6.226026 2.495151 -4.435085 H -14.470602 10.249865 2.623490

H -3.150707 2.590484 -6.723367 H -13.321804 9.745724 3.868626

H -3.435570 3.740658 -4.502973 H -12.739577 10.518456 2.385094

H -5.469730 3.448237 -3.179497 H -2.459203 5.023900 -0.153765

H 0.120107 2.122228 -1.332208 H -1.078672 3.964234 -0.397188

H -1.359525 1.810405 1.810080 C -0.447441 6.482093 -1.376663

H 0.516479 -0.578492 2.180148 H -0.835104 4.857358 -2.743254

H -1.510647 -1.773176 3.058825 H -2.216901 5.910986 -2.475532

H -2.812247 -1.950266 0.814513 H -13.411736 7.418525 13.459710

H -1.136021 -2.446017 0.831445 H -12.152531 8.288614 15.348370

H -2.508650 -0.404841 2.624469 H -10.556424 7.936750 14.478126

H -0.288801 0.343320 3.445736 C 0.097009 7.449880 -2.423119

H 0.361656 1.778024 1.459924 H -0.988955 7.044666 -0.604162

H 6.188192 0.916011 -1.716446 H 0.389003 5.987880 -0.863604

H 0.508208 0.344591 -3.250859 H 0.754335 8.198076 -1.968286

H 4.610996 1.657227 -6.415229 H 0.677267 6.925358 -3.191177

H 1.972169 1.564023 -4.878652 H -0.712745 7.987198 -2.930000

H 4.872124 -1.421447 -1.587061

H 2.524767 -2.665114 -1.598674 ! Third Vinyl Coordination/Insertion -

H 1.046889 -2.774946 -2.536874 Product !

H 3.189669 -2.603047 -3.939343 scf done: -1807.905992

H 1.967860 -1.408520 -4.331751 C 3.409293 -3.175117 -6.124757

H 3.738299 3.857675 -1.936240 C 2.635039 -3.659464 -4.924683

H 2.319873 2.913139 -2.362144 C 1.337130 -3.154817 -4.596909

H 5.087768 0.934395 0.475174 C 0.600496 -2.168620 -5.461268

H 3.444864 0.826298 1.284472 C 1.526020 -1.519368 -6.499766

H 7.891310 4.161147 3.343331 C 2.457174 -2.544874 -7.149938

H 6.890483 5.594026 3.509727 C 0.872091 -3.862037 -3.460839

H 8.604228 6.914872 2.214380 C 1.877924 -4.791964 -3.080982

H 9.600527 5.482146 2.094241 C 2.979200 -4.673404 -3.985693

H 9.739152 5.394620 4.639167 Zr 2.886734 -2.616303 -2.594839

8.781600 6.841682 4.734085 C 2.412312 0.491039 -2.939972

H -13.010629 8.041185 5.772576 C 3.246483 1.774269 -2.950518

H -11.653959 9.122134 5.902055 C 3.965758 2.037890 -4.273807

H -11.696301 6.240609 6.984948 C 4.279295 -5.431584 -3.896908 C 4.799434 -5.470991 -2.448346 H 1.577137 -3.648342 1.053422

C 4.710348 -4.121377 -1.782493 H 2.829459 -2.436026 2.881307

C 3.954478 -3.813416 -0.605963 H 4.357968 -1.084004 1.335982

C 4.109109 -2.423874 -0.308328 H -0.090770 -3.737356 -2.981630

C 4.924007 -1.867477 -1.327184 H 5.946861 -2.795271 -3.092070

C 5.302500 -2.908250 -2.225861 H 1.856457 -3.336963 -7.615386

C 3.615868 -1.802798 0.970802 H 4.174476 -2.434984 -5.842585

C 3.347649 -2.883976 2.027148 H 1.804905 -5.502912 -2.266206

C 2.524546 -4.038034 1.450287 H 4.212583 -6.188219 -1.865898

C 3.292285 -4.773377 0.345434 H 5.832758 -5.836381 -2.432523

C 1.742378 0.122576 -1.596855 H 4.155731 -6.453401 -4.277036

C 1.268262 -1.348551 -1.595679 H 5.021078 -4.951765 -4.543981

C 0.595162 1.111760 -1.305434 H 1.646071 0.535312 -3.726821

C -0.085133 0.968859 0.056284 H 3.115262 -0.313302 -3.281491

C -1.193276 2.006417 0.251760 H 0.336785 -1.419484 -2.175464

C -1.920798 1.920411 1.594405 H 1.015772 -1.675777 -0.578606

C -3.033301 2.965037 1.734886 H -2.350623 0.915773 1.718786

C -3.780271 2.933846 3.074690 H -1.198789 2.045632 2.414255

Al -5.272475 4.248880 3.277627 H -2.595115 3.961572 1.578161

C -5.836303 5.183519 1.601840 H -3.745266 2.828298 0.908160

C -7.072890 6.096975 1.573849 H -4.192518 1.925203 3.247012

C -6.915880 7.297461 2.508988 H -3.069810 3.081007 3.903443

C -6.022185 4.577545 5.095753 H -7.106303 4.746090 5.017560

C -5.740490 3.516564 6.169829 H -5.620113 5.548499 5.432987

C -6.288221 3.887263 7.551658 H -6.171505 2.551595 5.865190

C -6.043414 2.827199 8.626798 H -4.657981 3.342436 6.251455

C -6.578148 3.227745 10.002424 H -5.838994 4.839431 7.869366

C -6.350437 2.158641 11.081135 H -7.368009 4.077869 7.468851

C -6.909334 2.549964 12.416939 H -6.508767 1.879936 8.317506

C -6.202575 2.689594 13.538847 H -4.965110 2.624633 8.701371

C -8.353308 5.319920 1.885512 H -6.104529 4.165394 10.322793

H 2.502589 0.250718 -0.811199 H -7.653790 3.441126 9.927342

H 0.972829 2.139558 -1.389198 H -6.825454 1.222158 10.751222

H -0.160787 0.999657 -2.097495 H -5.277466 1.948107 11.176831

H 0.662934 1.077840 0.855128 H -5.945935 4.396828 0.837313

H -0.509293 -0.038102 0.163431 H -4.952757 5.753596 1.267636

H -0.765924 3.013390 0.139358 H -7.180400 6.496773 0.552502

H -1.927038 1.900646 -0.560715 H -9.242827 5.954979 1.799236

H 3.957828 -4.010407 -6.573190 H -8.484667 4.474654 1.199612

H 0.920238 -1.020040 -7.262590 H -8.335091 4.919447 2.907424

H -0.197773 -2.715525 -5.982021 H -7.767169 7.983850 2.429155

H 3.039208 -2.077105 -7.950375 H -6.849213 6.980568 3.557391

H 2.131050 -0.733126 -6.026609 H -6.010124 7.869961 2.275977

H 0.093261 -1.408174 -4.855870 H 2.592510 2.625205 -2.726308

H 5.263934 -0.838863 -1.374642 H 3.981184 1.733420 -2.134502

H 2.694594 -1.233940 0.800057 C 4.802884 3.318210 -4.261988

H 4.301548 -3.274536 2.405597 H 4.619795 1.185379 -4.515636

H 2.261582 -4.749842 2.239551 H 3.227282 2.097067 -5.085866

H 2.637369 -5.480822 -0.175408 H -7.983899 2.742509 12.444776

H 4.084993 -5.382053 0.803204 H -6.669619 2.983519 14.475626 H -5.128655 2.511569 13.563635

C 5.522570 3.579564 -5.581504

H 4.152568 4.170593 -4.024587

H 4.813358 3.677501 -6.411443

H 5.538870 3.261949 -3.448249

H 6.107645 4.504057 -5.539008

H 6.212768 2.764654 -5.830271

Examples: Long-Chain Branched Polyethylene via Coordinative Tandem Insertion and Chain-Transfer Polymerization Using rac-{EBTHI}ZrCl2/MAO/AI-alkenyl Combinations

In the following examples, the synthesis of LCB-PEs mediated by an /BuAI(oct-7-en-1-yl) activating agent is reported and their characterization by ¹³ C NMR spectroscopy and melt rheology is given. The efficiency of Al-alkenyl reactants (activating agents) as LCB promoters is reported, which operate via a tandem mechanism involving both coordination/insertion and transmetallation reactions, as corroborated by extensive DFT computations.

In situ synthesis of topologically modified linear polyethylenes using single-site polymerization catalysis is a challenging task but it can enable the production of valuable advanced polymer materials with tailored properties. Described herein is an efficient generation of long-chain branches (LCB) in linear polyethylenes using Al-alkenyl species, namely /BuAI(oct-7-en-1-yl) derived species (herein also named “AI-1”), in combination with homogeneous rac-{EBTHI}ZrCl2/MAO or heterogeneous MAO on silica-supported- rac-{EBTHI}ZrCl2/TIBAL catalytic systems.

As corroborated by extensive rheological studies and ¹³ C NMR spectroscopy, the Al- alkenyl reagent was found to be efficient in the formation of LCB, via a mechanistic pathway involving both insertion and transmetallation reactions. Formation of LCB has been rationalized by DFT computations carried out on the putative [rac-{EBTHI}Zr-R] ⁺ (R = Me, nPr, pentyl) cationic species and including a solvent model. Of the three possible isomers of Al/Zr heterobimetallic complexes derived from the cationic species [rac- {EBTHI}Zr-R] ⁺ and AI-1 , one was identified, on kinetic and thermodynamic grounds, as a key intermediate. The DFT showed that:

(i) insertion of ethylene into the Zr-alkyl bond of the growing PE chain is accompanied by a reversible decoordination of the Al-vinyl transfer agent (A VTA),

(ii) the vinyl 1 ,2-coordination/insertion of the alkenyl moieties of AI-1 into the Zr-alkyl bond, resulting in the formation of branching, is in direct kinetic competition with the insertion of ethylene, and

(iii) the re-coordination of the AVTA after either insertion step is thermodynamically favored and mostly responsible for the transmetallation phenomenon.

Example 1. Synthesis of Al-octenyl reagents (activating agents)

In order to prepare a mixed, well-defined isobutyl/oct-7-en-1-yl aluminum derivative, the hydroalumination reaction between DIBAL-H and a large excess of 1 ,7-octadiene was studied under two conditions (see also general information above and Figure 15). The average composition of the reaction mixture was assessed by ¹ H NMR spectroscopy, through integration of the signals corresponding to the AI-C/7 ₂ (-octenyl) and AI-C/7 ₂ (-'Bu) groups (5H 0.45 and 0.25 ppm, respectively; Figure 1). A series of signals corresponding to side-products was also detected. The principal side-product, identified as 7- methylenepentadeca-1 ,14-diene, can result from the 1 ,2-insertion of an octenyl moiety into Al-C bond followed by -H elimination.

The amount of side-product was determined from the ratio of the signal area at 5H 4.82 ppm (terminal =C/7 ₂ protons) to the total area of the C/7 ₂ -AI signals. Complete removal by a high-vacuum distillation of the side-product failed. Therefore, the original reaction conditions were optimized to minimize the formation of the undesired compound. Thus, by performing the reaction under slightly modified conditions (Procedure B: 85 °C, reaction time 16 h), the targeted product AI-1 (herein also corresponding to “Oct1.91ArBu1.09” or “Octi.gAl’Bui.i”), exhibiting the octenyl/'Bu ratio (m/n) close to 2 was obtained in a selective and reproducible manner (see Figure 2).

Example 2. Polymerization of ethylene catalyzed by homogeneous rac-

{EBTH l}ZrCI ₂ /MAO/AI-alkenyl systems.

In this example, rac-{EBTHI}ZrCI ₂ (herein also “Zr-1”, see formula A below) was selected as pre-catalyst.

Formula A

The polymerization of ethylene in the presence of Zr-1/MAO/AI-1 system was studied (Table 1). Compared to the benchmark reaction conducted without Al-promoter (entry 1), significantly lower productivities were achieved for the reactions performed at 40 °C (entries 2 and 3). The polymers isolated in these runs (PE2 and PE3) exhibited poor solubility in 1 ,3,5-trichlorobenzene at 135 °C and lower T _m and T _C r _ys t values (126-128 °C and 114 °C, respectively). The insolubility of these materials was attributed to the alleged formation of crosslinks promoted by AI-1. A soluble sample (PE4) characterized by SEC was obtained by carrying out the reaction at 60 °C in the presence of H ₂ (entry 4). The low M _w value of the polymer is likely due to the capability of both H2 and AI-1 to act as chaintransfer reagents, while the formation of crosslinks was probably suppressed due to the higher temperature, compared to entries 2 and 3 (60 and 40 °C, respectively).

Table 1 : Polymerization of ethylene in the presence of rac-{EBTHI}ZrCl2/MAO/AI-1 ^a Polymerization conditions: 300 mL-high pressure glass reactor; solvent: toluene, 150 mL; P(ethylene) = 4 bar; time = 15 min; [Zr]o = 10 pM, [AlMAo]/[Zr]o = 4,500. ^c Determined by DSC from second run. ^d Determined by SEC. ^e [AlMAo]/[Zr]o = 5,000. ^f H2 = 800 ppm.

In order to study the effect of AI-1 on the formation of LCB, the soluble samples (PE1 and PE4) were analyzed by ¹³ C NMR spectroscopy. A signal compatible with the CH- group at the branching point of the LCB (SCH 38.22 ppm) (Hsieh, T ; Randall, J. C. Ethylene-I-Butene Copolymers. 1. Comonomer Sequence Distribution, Macromolecules 1982, 15, 353-360) was observed in the spectrum of the sample synthesized with MAO only (Figure 3). Based on the integration of this signal, the LCB density was estimated to be 0.3/10,000C. However, some resonances related to the sample oxidation (that allegedly occurred under the analytical conditions, i.e. 135 °C) were also detected. The presence of these resonances may affect the accuracy of LCB quantification, hence the value found is considered as indicative.

¹³ C NMR spectroscopic analysis of the PE prepared in this example in the presence of Al- 1 did not allow to distinguish the tertiary carbon atoms of side-chains longer than 6 carbons. Both samples (PE1 and PE4) were therefore further examined by melt rheology. For this purpose, the trend of the modulus of the complex viscosity (|rf|) as a function of the angular frequency (co) was first investigated (Figure 16a). In the whole range of frequencies considered (0.1-250 rad.s ¹ ), the viscosity of the PE synthesized with MAO only (PE1 , entry 1) was higher than that of the sample prepared in the presence of AI-1 (PE4, entry 4). The van Gurp-Palmen (vGP) plot was next considered (Figure 16b). In this representation, curves of purely linear polymers tend to a phase angle (5) of 90 ⁰ at low |G*|, while lower angles are observed upon increasing the LCB density and/or broadening of the molecular weight distribution (MD).(Trinkle, S.; Friedrich, C. Van Gurp- Palmen-plot: a way to characterize polydispersity of linear polymers, Rheol. Acta 2001 , 40, 322-328; Trinkle, S.; Walter, P.; Friedrich, C. Van Gurp-Palmen Plot II - classification of long chain branched polymers by their topology Rheol. Acta 2002, 41, 103-113). The curves for both PE1 and PE4 were found to be far from the linear case, which is consistent with the above ¹³ C NMR spectroscopy results and a significant presence of LCB. However, the polymer prepared with AI-1 (PE4) showed lower phase angle than that of the PE synthesized with MAO only. Given that the polydispersity values of these two polymers were found to be rather similar (/W _w //W _n = 3.3-3.6), the drop of 5 could be ascribed only to an increase of LCB content. The presence of LCB also in the PE produced in the absence of the Al-alkenyl promoter (PE1) can be explained by the fact that the pre-catalyst herein employed is known to promote the formation of branches to a certain extent via macromonomer insertion (Malmberg, A.; Kokko, E.; Lehmus, P.; Lofgren, B.; Seppala, J.V. Long-Chain Branched Polyethene Polymerized by Metallocene Catalysts Et[lnd] ₂ ZrCI ₂ /MAO and Et[lndH ₄ ] ₂ ZrCI ₂ /MAO, Macromolecules 1998, 31, 8448-8454).

Example 3. Polymerization of ethylene catalyzed by heterogeneous supp-rac- {EBTHI}ZrCI ₂ /TIBAL/AI-1 systems.

The ability of AI-1 (as described above) to promote LCB was also explored under heterogeneous conditions by employing the MAO on silica-supported version of the catalyst (herein also named “supp-Zr-1”). This supported catalyst was prepared as indicated above. Polymerisation was carried out as described above under the general information.

EXPERIMENT 1

A first set of reactions was performed in a 300 mL-reactor at 80 °C in the presence of 800 ppm of H ₂ as re-activator/chain-transfer agent (Table 2).

In polymerization runs PE6 to PE14 the amounts of alkenyl-aluminum activating agent applied during different reactions ranged from 20 to 3000 ppm (see Table 2). Once the alkenyl-aluminum agent was prepared and purified, a 10 wt% solution in /so-hexane was made thereof and used to prepare a catalyst suspension. A catalyst suspension (mixture) comprising the catalyst compound and the activating agent solution was prepared in a syringe and this premix was injected in the reactor. In runs PE12-PE14, TIBAI co-catalyst was further added to the catalyst suspension mixture.

Polymerization started upon catalyst suspension injection, was performed at 80 °C in the presence of 800 ppm of H ₂ , and was stopped after 1 h by reactor depressurization. Reactor was flushed with nitrogen prior opening and the polymer was collected by filtration, washed with methanol (200 mL) and dried under reduced pressure at 65 °C overnight.

For run PE5 of Table 2, polymerization was carried out in a same was as for PE6 to PE14 with the difference that no alkenyl-aluminum agent was added. Table 2 indicates the reaction conditions as applied in the different polymerization reactions of this example and properties of the obtained ethylene polymers. The polymerisation reactions were all run in the presence of hydrogen (800 ppm). Ppm values in Table 2 are expressed by weight. Table 2. Polymerization of ethylene in the presence of supp- Zr-1/TIBAL/AI-1 ^a Polymerization conditions: solvent: toluene, 150 mL; T _poi = 80 °C; P(ethylene) = 4 bar; time = 60 min; supp-Zr-1 = 35 mg ([Zr]o = 14 pM); H2 = 800 ppm. ^b Determined by DSC from second run (see above under “general information”). ^c Determined by SEC (see above under “general information”).

For comparison purposes, a benchmark polymerization was carried out with only TIBAL as scavenger (PE5). Ethylene polymerizations were performed by increasing progressively the amount of AI-1 (PE6-PE11) and also by using mixtures of TIBAL/AI-1 (PE12-PE14). All polymerizations showed the same productivity, regardless of the amount of AI-1 used. In addition, thermal properties of the ethylene polymers (PEs) were found to be similar. Rheological fingerprints of the samples were found to be highly affected by the use of AI-1. In fact, all samples prepared with the activating agent exhibited higher |q*| at low frequencies and stronger shear thinning as compared with those PE5 (see Figure 17 a,b). Moreover, the magnitude of such variations was consistent with the amount of AI-1 employed. Since, in this case, M _w effect can be excluded, the different rheological behaviors can be confidently attributed entirely to LCB formation. This assumption was confirmed by the vGP plots (see Figure 17 c,d).

All polymers show a decreasing delta towards the points with the lowest frequency. It is assumed to be in proximity of a minimum which cannot be observed due to the limited range of frequencies investigated. The presence of a minimum in vGP plots has been already reported in literature. The dlog|r|*|/dlog co vs. 5 plot for samples PE5-PE14 is shown in Figure 6.

EXPERIMENT 2

The effect of H2 on the process and polymer properties was also investigated. For this purpose, a second series of polymerization tests was carried out in the presence of a fixed amount of AI-1 ('Bui.09AI(1-oct-7-en-yl)i.9i; as described above) and variable amounts of H2 (Table 3). In order to achieve higher activity, 1-hexene was added as co-monomer (cf. entries 3 and 4) (Yang, Q.; Jensen, M. D.; McDaniel, M. P. Alternative View of Long Chain Branch Formation by Metallocene Catalysts, Macromolecules 2010, 43, 8836-8852). Under these reaction conditions, a drop of productivity and a decrease of the polymer molecular weight were observed, as the amount of H2 in feed was increased; in fact, if too much H2 is added, it rather behaves as a chain-terminating agent. On the other hand, the T _m and polydispersity values were not significantly altered (except for the run conducted in the absence of the co-monomer), spanning in the ranges of 120-122 °C and of 2.8-3.3, respectively. Excessively increasing the amount of H2 had also a detrimental effect on LCB formation, as highlighted by their corresponding vGP plots (Figure 18). In that case, the phase angle 5 increased with the amount of H2 introduced, suggesting a drop of LCB density (Yang et al. 2010). The dlog|r|*|/dlog co vs. 5 plots for samples PE15-PE22 appeared to be generally linear (see Figure 7)). This could be attributed to the occurrence of side processes (chain-transfer, termination) competing at higher H2 concentrations with monomer insertion and transmetallation reactions, preventing both the growth of the main PE chain and LCB formation. Table 3. Effect of H2 concentration on the polymerization of ethylene in the presence of supp-

Zr-1/AI-1 ^a Polymerization conditions: solvent: /so-butane 41.25 g; T _poi = 85 °C; P(ethylene) = 25 bar (6 wt%); 1-hexene 2.44 wt%; time = 60 min; supp-Zr-1 = 5.0 mg ([Zr]o = 2.0 pM). ^b Determined by DSC from the second run (see under general information above). ^c Determined by SEC (see under general information above). ^d No 1-hexene added. ^e co-reactant here means TIBAL or AI-1.

The polymers isolated in entries 3 and 4 were further analyzed by ¹³ C NMR spectroscopy (Figures 4 and 5, respectively). However, resonance diagnostic for LCB (5 38.27 ppm) could not be observed for these entries suggesting that rheological studies appear more suitable for the detection of low amounts of branches in these examples.

Example 4. DFT studies on LCB formation

Usually, the influence of an organoaluminium reagent in the polymerization process is not taken into account by a standard computational model. This is due to the assumption that such a co-catalytic species simply delivers the alkyl group to initiate the polymerization. In this DFT study, it was aimed at rationalizing the mechanism of formation for long-chain branches during polymerization of ethylene with rac-{EBTHI}ZrCl2 carried out in the presence of an activating agent. /BuAI(oct-7-en-1-yl)2 (in this example also below denoted as “AI-1”) was applied for this simulation in this DFT study (Figure 19).

Figure 19 provides an outline of the stepwise protocol produced to gain further insights into possible mechanisms of branching in polyethylene. Three main investigations (highlighted steps in bold and underlined) were conducted, in respective order, concerning: 1) the initial coordination of the co-catalyst (in this example used as synonym for the activating agent) to the catalyst. 2) The resulting effects on ethylene polymerization. 3) The control the co-catalyst may introduce on the mechanism of insertion.

The first three ethylene insertions were computed with the cationic form of the active catalyst [rac-{EBTHI}ZrMe] ⁺ (Figure 8). The reaction was found to be favored both kinetically and thermodynamically (highest barrier of 6.8 kcal mol ¹ for the first insertion and exothermic by ~20 kcal mol ¹ each step). This is in line with the experimental ability of the EBTHI-Zr catalyst to efficiently polymerize ethylene. However, the overall situation is different when AI-1 is introduced in the polymerization due to the presence of, not only an alkyl but also, alkenyl chains on the co-catalyst. It was then suggested that AI-1 could coordinate to the [rac- {EBTHI}ZrMe] ⁺ catalyst generating an Al/Zr heterobimetallic species. Depending on the nature of the ‘bridge’ formed between the Zr and Al atoms, upon the binding of AI-1 to [rac- {EBTHI}ZrMe] ⁺ , three different isomers can be distinguished (Figure 20).

A comparison of the various coordination affinities between the three isomers and the parent [rac-{EBTHI}ZrMe] ⁺ system showed isomer A to be the most stabilized, with the bimetallic complex gaining 4.8 kcal mol ¹ . Although the stabilizing effect is rather small, the influence of the co-catalyst coordination on the ethylene polymerization needed to be investigated. It was found that two pathways for insertion of an ethylene monomer exist: after dissociation (Figure 21) or whilst AI-1 remained coordinated (Figure 9).

The two respective barriers for the first insertion of ethylene, once the co-catalyst is dissociated or remaining coordinated to the [rac-{EBTHI}ZrMe] ⁺ system, were 9.0 kcal mol ¹ and 46.0 kcal mol ¹ . In these cases, nucleophilic addition of ethylene occurs about the Zr-Me or Al-Me bond respectively. The non-dissociative profile (Figure 9) refers to the less likely insertion of ethylene caused by a nucleophilic addition from the methyl group towards the monomer - catalyst system. The ‘classical insertion’ refers to the addition of ethylene to the Zr-Me bond once AI-1 has dissociated, via cleavage of the Zr-Me-AI bridge. As a result, the insertion of ethylene via a systematic dissociation of the co-catalyst is kinetically preferable (Figures 10 and 11). Interestingly, regardless of the pathway ethylene is inserted, the re-coordination of the co-catalyst is thermodynamically most favorable, affording the same [rac-{EBTHI}Zr-(n- propyl)-AI(oct-7-en-1-yl)2/Bu] ⁺ bimetallic species.

Because dissociation of the AI-1 species is favorable for ethylene insertions, a more thorough investigation into how this occurs was conducted. The mechanism of dissociation is thought to have two possibilities, identifying that either the Al— alkyl or AI-(oct-7-en-1-yl) bond is cleaved (Figure 22). Cleavage of the AI-(oct-7-en-1-yl) bond (pathway 2) owes to an alkenyl chain-shuttling from the co-catalytic species to the catalyst system forming the [rac-{EBTHI}Zr-(oct-7-en-1-yl)] ⁺ species. An investigation was conducted into the required energy input needed to cleave either the Al-methyl or Al-alkenyl bonds. It was concluded that the Al-alkenyl bond was slightly stronger, with a dissociation energy of 6 kcal mol ¹ relative to 4.8 kcal mol ¹ for the Al-methyl bond. A difference of 1.2 kcal mol ¹ gives little concrete evidence of one bond cleavage being definitively favorable from the another but may offer insight into a competitive environment that allows the co-catalytic species to dissociate. An Al-alkenyl group transfer to form [rac- {EBTHI}Zr-(oct-7-en-1-yl)] ⁺ species brings about a Zr-polymeryl moiety with a terminal vinyl group after one step (considering the formation of the bimetallic species as a reference).

Considering the length of the alkenyl chain, an intramolecular cyclisation was considered and investigated. It was found that subsequent insertions of ethylene into the [rac-{EBTHI}Zr-(oct- 7-en-1-yl)] ⁺ chain are plausible (Figure 23) and, although a cyclisation is feasible, it is kinetically less favorable than the adduct-less insertions of ethylene (with a corresponding transition state barrier difference of 7.2 kcal mol ¹ ; Figure 12). This gives sufficient evidence to suggest that an Al-alkenyl chain transfer provides a significantly more facile one-step precursor to longer chain formations. In comparison to a cyclisation reaction, the ethylene insertions are far more likely and the adduct-less nature of this owes to a faster generation of a linear Zr-polymeryl species.

The cleavage of the Al— alkyl bond results in a competition between the insertion of ethylene monomer and dissociation of the AI-1 moiety. Therefore, the subsequent insertions will occur in a three-step process: 1) dissociation of co-catalyst 2) insertion of ethylene 3) re-coordination of AI-1 to form the more stable bimetallic species. Thus far in this study, we have highlighted that the dissociation of AI-1 is preferable prior to the insertion of ethylene. Hence, the next comparison to be made was the potential effects that subsequent insertions induce and examine whether the length of the alkyl/polymeryl chain R on the [rac-{EBTHI}Zr-R] ⁺ system affects either the incorporation of AI-1 , the insertion of ethylene, or both. The computed coordination energies for the growing polymer chain generated via first, second and third ethylene insertions are summarized in Table 4.

Table 4. A comparison between the respective coordination/re-coordination energies of the co-catalyst and monomer species.

The presence of AI-1 provides a stabilizing interaction with [rac-{EBTHI}Zr-R] ⁺ throughout each insertion step. Generally, the extent to which the co-catalyst stabilizes the bimetallic species seems to decrease as the Zr-R chain length increases. In contrast, ethylene coordination provides little, if any, stabilizing effects and thus a competition between the alkenyl moiety of the co-catalyst and monomer becomes more prevalent as the polymer chain grows.

Since AI-1 possesses two alkenyl chains with a terminal vinyl group that may compete with the ethylene coordination, once the co-catalyst has dissociated, the coordination and subsequent insertions of the vinyl group from oct-7-en-1-yl was investigated (Figure 24).

In order to highlight the competition present within this model, a comparison was made between the adducts formed from the active [rac-{EBTHI}Zr-R] ⁺ catalyst and ethylene, and those leading to the vinyl group 1 ,2-insertions. For the sake of clarity, the following profile (Figure 25) demonstrates the effects when a competitive environment is most significant: the third insertion of ethylene vs. a vinyl 1 ,2-coordination/insertion to the [rac- {EBTHI}Zr-(n-pentyl)] ⁺ system.

The adducts produced by either monomer or co-catalyst coordination differ greatly, whereby the initial interaction of ethylene is destabilizing (+4.0 kcal mol ¹ ) and the vinyl group coordination could arguably be in an equilibrium with the bimetallic resting state. Nevertheless, the vinyl coordination is much more stabilizing, and therefore favored, in comparison to the ethylene monomer. This concept is also in agreement with the weak coordination/dissociation proposal of the AI-1 co-catalyst (activating agent). Kinetically, comparing the transition state barriers in Figure 25, one observes that the vinyl 1 ,2- coordination/insertion pathway is in direct competition with the insertion of ethylene. The vinyl group 1 ,2-insertions generally become more viable as the chain length increases, referring to the competitive kinetics of the first, second and now third insertions of ethylene (Figures 12 and 13). Although the stabilities of the products differ, it is an interesting propensity that the vinyl coordination to the catalyst produces a more stable adduct, relative to the ethylene coordination/insertions. Therefore, the present model suggests a growing competition that kinetically favors the formation of a branched product over a linear polymer.

In conclusion, the above examples show that an Al-alkenyl compound as defined herein has been synthesized and employed as a LCB-promoter in the polymerization of ethylene catalyzed by homogeneous rac-{EBTHI}ZrCl2/MAO or heterogeneous MAO on silica- supported-rac-{EBTHI}ZrCl2/TIBAL catalytic systems. The use of this Al-based co-reagent induces a marked change in the rheological behavior of the PEs consistent with LCB generation. The intermediacy of Al/Zr heterobimetallic species, resulting from reversible coordination of AI-1 to [rac-{EBTHI}Zr-R] ⁺ , was established and for the first time scrutinized in details by DFT computations.

MATERIALS applicable to the below examples 5 to 9

In examples 7 and 8 (isobutyl)i.5(oct-7-en-1-yl)i.5aluminum, herein also denoted as Octi.5AI'Bui.5, was used. This compound can be obtained when following the procedure as described in Nam Y-G et al. (Macromolecules 2002, 35, pages 6760-6762).

In example 9, (isobutyl)i.09(oct-7-en-1-yl)i.9ialuminum, herein also denoted as Octi.9iAI'Bui.o9 (or Octi.gAl'Bui.i), hence with octenyl/isobutyl ratio close to 2, was used. This compound was prepared as follows:

Under an Ar atmosphere, a Schlenk flask equipped with a magnetic stir bar was charged with 1 ,7-octadiene (20 mL, 14.9 g, 135 mmol, 10 equiv.) and DIBAL-H (11.7 mL of a 1.2 M solution in toluene, 13.5 mmol, 1 equiv.) was added dropwise. The mixture was stirred at 110 °C for 1 h and then at 85 °C for 16 h. Volatiles were removed under reduced pressure affording a colourless oil. The composition of the reaction mixture was determined by ¹ H NMR spectroscopy. The compound was found to be 'Bui.09AI(1-oct-7- en-yl)i.9i.

Example 5: Preparation of Supported Catalyst Compound A rac-ethylene-bis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride (CAS Number 100163-29-9) (see below formula X) was used as metallocene component supported on silica which has been previously activated with methylalumoxane (MAO) as described below.

Formula X

MAO treatment

Methylaluminoxane (30 wt%) (MAO) in toluene (obtained from Albemarle) was used as the activator. Silica (from PQ corporation; D50= 50 pm) was used as catalyst support and it was dried at 450 °C under nitrogen for 6 h.

10 g of the dried silica was introduced in a 500 mL round-bottomed flask. Toluene was added and the suspension was stirred at 100 rpm. MAO (30 % by weight in toluene) was dropwise added via a dropping funnel and the resulting suspension was heated at 110 °C (reflux) for 4 hours. The amount of added MAO was calculated in order to reach the desired Al loading. After the reflux, the suspension was cooled down to room temperature and the mixture was filtered through a glass frit. The recovered powder was washed with toluene and pentane before being dried under reduced pressure overnight.

Metallocene treatment

In a 250 mL round bottom flask, 9.8 g of the above-obtained MAO-support was suspended in 80 mL of toluene. Then, 0.2g of rac-ethylene-bis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride (formula X) (CAS Number 100163-29-9) was dissolved in 20 mL of toluene and slowly added to the suspended silica-containing support . The resulting suspension was stirred at 100 rpm for 2 hours at room temperature. Solvent was removed by filtration. The obtained catalyst was washed with /so-hexane, filtered and dried at room temperature.

Example 6: Preparation of Supported Catalyst Compound B (comparative example)

MAO treatment

Methylaluminoxane (30 wt%) (MAO) in toluene (obtained from Albemarle) was used as the activator. Silica (from PQ corporation; D50= 50 pm) was used as catalyst support and it was dried at 450 °C under nitrogen for 6 h.

10 g of the dried silica was introduced in a 500 mL round-bottomed flask. Toluene was added and the suspension was stirred at 100 rpm. MAO (30 % by weight in toluene) was dropwise added via a dropping funnel and the resulting suspension was heated at 110 °C (reflux) for 4 h. The amount of added MAO was calculated in order to reach the desired Al loading. After the reflux, the suspension was cooled down to room temperature and the mixture was filtered through a glass frit. The recovered powder was washed with toluene and pentane before being dried under reduced pressure overnight.

Metallocene treatment

0.2 g of Bis(n-butylcyclopentadienyl)zirconium(IV) dichloride (formula Y) (CAS Number 73364-10-0) was dissolved in toluene and 10 g of the above-obtained MAO-support was slowly added, and the resulting suspension was mixed for 2 h at room temperature. Solvent was removed by filtration. The obtained catalyst was washed with iso-hexane, filtered and dried at room temperature.

Formula Y

Example 7: Polymerization reaction for preparing ethylene-hexene copolymers

In this example, the effect of using a catalyst system according to the invention on the preparation of ethylene polymers with long chain branches is demonstrated. Copolymerisation reactions according to the invention of ethylene with hexene-1 were carried out using Octi.sAl'Bui.s as activating agent in the presence of the supported bridged catalyst as described in example 5 (Catalyst Compound A) (Runs 1 to 5).

Comparative copolymerisation reactions of ethylene with 1 -hexene were also carried out using Octi.sAl'Bui.s as activating agent in the presence of the supported non-bridged catalyst as described in example 6 (Catalyst Compound B) (Runs 6 to 10).

Comparative copolymerisation reactions of ethylene with 1 -hexene were also carried out in the presence of the supported bridged metallocene of example 5 (Compound A) and example 6 (Compound B) but in the absence of Octi.sAl'Bui.sas activating agent) (Comparative Runs CR1 and CR2, respectively).

Polymerization reactions were performed under slurry conditions in a 130 ml autoclave reactor with an agitator, a temperature controller and inlets for feeding of ethylene, comonomer and hydrogen. Prior to being used the reactor was heated at 110 °C and flushed with nitrogen during 1 h and then cooled to 40 °C.

For runs R1-R5 of Table 5, the reactor was loaded with 75 mL of isobutane, 1 .6 mL of 1- hexene and pressurized with 23.8 bar of ethylene with 800 ppm of hydrogen. Catalyst compound A (5.16 mg), prepared as described above in example 5, was contacted with Octi.5AI'Bui.5. Amounts of alkenyl-aluminum activating agent applied during different reactions in these runs ranged from 50 to 500 ppm. Once the Octi.sAl'Bui.s compound was prepared and purified, a 10 wt% solution in /so-hexane was made thereof and used to prepare a catalyst suspension. A catalyst suspension (premix) comprising the catalyst compound A, 1-hexene and the Octi.sAl'Bui.sSolution was prepared in a syringe and this premix was injected in the reactor. Polymerization started upon catalyst suspension injection, was performed at 85 °C and was stopped after 1 h by reactor depressurization. Reactor was flushed with nitrogen prior opening and the polymer was dried at 50 °C overnight under reduced pressure.

For runs R6-R10 of Table 5, the reactor was loaded with 75 mL of isobutane, 1 .6 mL of 1-hexene and pressurized with 23.8 bar of ethylene with 800 ppm of hydrogen. Catalyst compound B (1.98 mg), prepared as described above in example 6, was contacted with the activating agent. Amounts of alkenyl-aluminum (Octi.sAl'Bui.s) activating agent applied during different reactions in these runs ranged from 50 to 500 ppm. Once the Octi.sAl'Bui.sCompound was prepared and purified, a 10 wt% solution in /so-hexane was made thereof and used to prepare a catalyst suspension. A catalyst suspension (premix) comprising the catalyst compound B, 1-hexene and the alkenyl-aluminum solution was prepared in a syringe and this premix was injected in the reactor. Polymerization started upon catalyst suspension injection, was performed at 85 °C and was stopped after 60 minutes by reactor depressurization. Reactor was flushed with nitrogen prior opening and the polymer was dried at 50 °C overnight under reduced pressure.

For runs CR1 and CR2 of Table 5, the reactor was loaded with 75 mL of isobutane, 1 .6 mL of 1-hexene and pressurized with 23.8 bar of ethylene with 800 ppm of hydrogen. Catalyst Compound A (5.31 mg) or Catalyst Compound B (1.98 mg) respectively, were prepared as described above, and contacted with TIBAI as a 10 % by weight solution in iso-hexane. Polymerization started upon catalyst suspension injection, prepared in a same way as described above for runs R1 to R10, was performed at 85 °C and was stopped after 1h by reactor depressurization. Reactor was flushed with nitrogen prior opening and the polymer was dried at 50 °C overnight under reduced pressure. Table 5 indicates the reaction conditions as applied in the different polymerization reactions of this example. The ppm values in Table 5 are expressed by weight. Table 6 reports properties of ethylene polymers obtained in this experiment.

Table 5 (*) as compared to the Comparative Run using the same catalyst compound

Table 6 Runs 1 to 5

The results shown in Table 6, indicate that the activity in the different polymerisation reactions according to the invention is relatively well maintained when adding activating agent and remains relatively constant, and shows an optimum (relative activity about 88%) around 200 and 300 ppm of activating agent in this example. It is also observed that melt indices decrease steadily with increasing amounts of activating agent.

The reported activity, MI2 values, g _r heo values, and van Gurp-Palmen plots obtained in the present experiment for runs 1 to 5 were considered as indicators of good activity and presence of LCBs in the obtained polymers. g _r heo values were determined for the polymers of the comparative example CR1 and runs R1 to R5. All reported values are below 1 , pointing to the presence of LCB. The data obtained shows that g _r heo values decrease, pointing to an increase in LCBs, with increasing amounts of activating agent. All resins in which the activating agent was applied gave a grheo value that is clearly below 1.0. van Gurp-Palmen plots were established for the examples of Runs 1 to 5 and are reported in Figure 27. In these experiments, the van Gurp-Palmen plots indicate that polymers produced under conditions in which activating agent was added induces the formation of LCBs. When comparing the reference reaction (CR1) with reactions in which activating agent was applied, it can be seen that the latter reaction tends towards lower phase angles at lower values of complex moduli, which is an indication for the presence of long chain branches. The plots of figure 27 also illustrate increasing amounts of LCBs when applying increased amounts of activating agent.

Figure 28 represents GPC profiles of ethylene resins of CR1 and Runs 1 to 5. GPC data shows occurrence of a “shoulder” like pattern in the higher values of M, which further confirms the presence of LCBs. An interesting additional effect was that longer chains were produced with increasing amounts of alkenyl-aluminum compound.

Runs 6 to 10 grheo values were determined for the polymers of the comparative example CR2 and runs R6 to R10. Figure 29 represents a van Gurp-Palmen plot (phase angle versus complex shear modulus) of ethylene resins of CR2 and Runs 6 to 10. Based on the g _r heo values and the van Gurp-Palmen plots it is noted that the catalyst system as applied, i.e. including a non-bridged supported metallocene catalyst (compound B) combined with an activating agent, has no influence on the formation of LCB. The catalyst system as applied in runs 6 to 10 also did not influence the GPC data and profiles for the resulting ethylene polymers, and this regardless of the quantities of activating agent used. Summarised, comparing runs R1 to R5 with CR1 run, shows that the use of a catalyst system according to the invention, i.e. using an alkenyl-aluminum agent in combination with supported catalyst compound A, permits to prepare polyethylene having LCBs. The amounts of LBCs formed is correlated to the amount of activating agent introduced in the reactor, hence providing a means for steering LBC concentration. The results of this example also indicate that, with increasing amounts of activating agent applied, the T _m remains relatively constant.

Comparing the different catalyst systems as applied in these examples (R1 to R5 compared to R6 to R10), good result on LCB formation were obtained through a combined application of an alkenyl-aluminum compound as defined herein as activating agent and a heterogenous bridged metallocene catalyst as defined herein.

Summarised, above example 7 illustrates that when using a catalyst system according to the invention, including a supported bridged metallocene catalyst as defined herein in combination with an alkenyl-aluminum compound as activating agent as defined herein:

Polymerization activity is maintained and remains relatively constant when using different amounts of activating agent.

Ethylene polymers having long chain branches are obtained.

There is a positive correlation between quantity of activating agent and amount of formed long chain branches.

Example 8: Co-polymerization of ethylene

In this example, the effect of using a catalyst system according to the invention on the preparation of ethylene-hexene copolymers with long chain branches is demonstrated. Copolymerisation reactions according to the invention were carried out using Octi.sAl'Bui.s as activating agent in the presence of the supported bridged catalyst as described in example 5 (Catalyst Compound A) (Runs 11 to 17).

Polymerization reactions in this example were performed under similar conditions as reported in example 7. Table 7 indicates the reaction conditions as applied in the different polymerization reactions of this example. The ppm values in Table 7 are expressed by weight. The properties of the obtained ethylene copolymers are reported in Table 8.

Table 7

Table 8

The present example demonstrates the formation of LCBs in co-polymerization reactions of ethylene with hexene when using a catalyst system according to the invention. The example further indicates that the alkenyl-aluminum activating agent and the alkylaluminum co-catalyst can be applied in combination. In this example the sum of the amounts of alkenyl-aluminum activating agent and the alkylaluminum was kept constant (200 ppm) in those reactions were both compounds were applied. Table 7 indicates the activity obtained in the different reactions (the more TIBAI used, the higher the activity), and the g _r heo value (indicative for LCB formation) obtained for the various polymers. Higher amounts of alkenyl-aluminum activating agent lead to more LCBs as shown by decreasing g _r heo values. An estimation of the level of LCB was also performed by plotting a van Gurp- Palmen plot of the obtained data (Figure 30). This example shows that both activating agent and alkylaluminum co-catalyst can be used in combination, and that depending on the ratio activating agent/alkylaluminum cocatalyst used, a certain balance in properties, i.e. level of activity and tailored formation of LCB, can be obtained.

Example 9: Homopolymerisation of ethylene

In this example, the effect of using a catalyst system according to the invention on the preparation of ethylene homopolymers with long chain branches is demonstrated.

Homopolymerisation reactions according to the invention were carried out using Octi.9iAI'Bui.o9, as activating agent in the presence of the supported bridged catalyst as described in example 5 (Catalyst Compound A) (Runs 18 to 26).

A comparative homopolymerisation reaction was carried out in the presence of the supported bridged metallocene of example 5 (Compound A) but in the absence of the alkenyl-aluminum activating agent (Comparative Run CR3).

Polymerization reactions were performed in a 300 mL high-pressure glass reactor equipped with a mechanical stirred (Pelton turbine) and externally heated with a double mantle with thermostated circulating water bath. The reactor was purged three times (vacuum-argon cycles) and charged with toluene (150 mL). MAO (1.5 mL of a 30wt% solution in toluene) and ethylene were introduced. The system was thermally equilibrated at the desired temperature for 30 min. Ethylene pressure was decreased to 1 bar and a a mixture of the supported catalyst and co-activators (TIBAL and/or alkenyl-aluminum compound) in toluene (ca. 2 mL) was injected. The ethylene pressure was increased to 4 barg (kept constant by means of a back regulator) and the reaction mixture was stirred for the desired time. The temperature inside the reactor was monitored using a thermocouple. The polymerization was stopped by venting the reactor and quenching with a 10 wt% solution of aqueous HCI in methanol (ca. 3 mL). The polymer was precipitated from methanol (200 mL) and 35 wt% aqueous HCI (2 mL) was added to dissolve possible catalyst residues. The polymer was collected by filtration, washed with methanol (200 mL) and dried under reduced pressure at 65 °C overnight.

In polymerization runs R18 to R26 the amounts of alkenyl-aluminum activating agent applied during different reactions ranged from 20 to 3000 ppm (see Table 9). Once the alkenyl-aluminum agent was prepared and purified, a 10 wt% solution in /so-hexane was made thereof and used to prepare a catalyst suspension. A catalyst suspension (mixture) comprising the catalyst compound and the activating agent solution was prepared in a syringe and this premix was injected in the reactor. In runs R24-R26, TIBAI co-catalyst was further added to the catalyst suspension mixture. Polymerization started upon catalyst suspension injection, was performed at 80 °C in the presence of 800 ppm of H2, and was stopped after 1 h by reactor depressurization. Reactor was flushed with nitrogen prior opening and the polymer was collected by filtration, washed with methanol (200 mL) and dried under reduced pressure at 65 °C overnight. For run CR3 of Table 9, polymerization was carried out in a same was as for Runs R24 to R26 with the difference that no alkenyl-aluminum agent was added.

Table 9 indicates the reaction conditions as applied in the different polymerization reactions of this example and properties of the obtained ethylene polymers. The polymerisation reactions were all run in the presence of hydrogen (800 ppm). Ppm values in Table 9 are expressed by weight.

Table 9 (*) as determined by DSC from second run. In this example DSC measurements were performed on a SETARAM Instrumentation DSC 131 differential scan calorimeter at a heating rate of 10 °C. min ^-1 ; first and second runs were recorded after cooling to 30 °C; the melting and crystallization temperatures reported in tables were determined on the second run.

(**) as determined by SEC. In this example, SEC analyses as described above were carried out in 1 ,2,4-trichlorobenzene at 135 °C using polystyrene standards for universal calibration.

The present example demonstrates the formation of LCBs in homopolymerization reactions of ethylene when using a catalyst system according to the invention. All polymerizations showed a similar productivity, regardless of the amount of activating agent used. In addition, the thermal properties of the ethylene polymers were found to be similar.

An estimation of the level of LCB was performed by plotting a van Gurp-Palmen plot (Figure 31). The rheological fingerprints of the different runs were found to be highly affected by the use of activating agent. Compared to the polymer obtained in the presence of TIBAI only (CR3), the materials synthesized with the activating agent showed lower phase angles at low G* values. The decrease of such angle is consistent with the increasing amount of Octi.9iAI'Bui.o9 employed. This trend can be attributed to the presence of LCBs.