Metal complexes comprising a guanidine and a thiophene-fused cyclopentadienyl ligand

Abstract

A metal complex of the formula (1) TCyLMZp (1) wherein M is a Group 4 metal, Z is an anionic ligand, p is a number from 1 to 2, preferably 2, TCy is a thiophene-fused cyclopentadienyl type ligand of the formula (2).

Description

Technical Field

[0001] The present invention relates to a metal complex comprising a certain thiophene-fused cyclopentadienyl group and an amidine ligand, a catalyst system containing said metal complex, and a method for manufacturing a polymer wherein said metal complex or catalyst system is used. Background Technology

[0002] Methods for polymerizing at least one olefin having 2 to 8 carbon atoms are known from KR20170046462 in the presence of a polymerization catalyst component comprising a benzothiophene-fused cyclopentadienyl group and an amidine ligand.

[0003] Surprisingly and advantageously, it was observed that the catalyst component with certain thiophene-fused cyclopentadienyl and amidine ligands produced polymers with higher molecular weights and in higher yields compared to KR20170046462.

[0004] The object of this invention is to provide novel catalyst components that offer higher molecular weight capabilities compared to catalyst components in known methods embodied in KR20170046462. Summary of the Invention

[0005] This objective is achieved through a metal complex of formula (1).

[0006] TCyLMZ p (1),

[0007] in

[0008] M is a group 4 metal.

[0009] Z is an anionic ligand.

[0010] p is a number from 1 to 2, preferably 2.

[0011] TCy is a thiophene-fused cyclopentadienyl ligand of formula (2).

[0012]

[0013] in

[0014] R 1 and R 2 Selected from the following groups respectively: hydrogen, halogens (especially Cl or Br), C1-C 10 -alkyl, C5-C 10 -Cycloalkyl, unsubstituted or C1-C 10 -alkyl or C1-C4-dialkylamino substituted C6-C 10-aryl (especially phenyl substituted with C1-C4-alkyl or C1-C4-dialkylamino groups), and SiR3, OR, NR2, SR, PR2, where R represents C1-C4-alkylamino groups respectively. 10 -alkyl, C5-C 10 -Cycloalkyl and unsubstituted or C1-C 10 -alkyl or C1-C4-dialkylamino substituted C6-C 10 -aryl, especially phenyl substituted with C1-C4-alkyl, especially R 1 and R 2 Selected from the following groups respectively: hydrogen, halogens (especially Cl or Br), C1-C 10 -alkyl, C5-C 10 -Cycloalkyl, unsubstituted or C1-C 10 -alkyl or C1-C4-dialkylamino substituted C6-C 10 -aryl, especially phenyl or alkyl substituted with C1-C4-alkyl or C1-C4-dialkylamino groups.

[0015] R 1 and R 2 Together with the two double-bonded carbon atoms of the thiophene ring to which they are attached, they form unsubstituted or C1-C4-alkyl-substituted aliphatic C5-C6-cyclic olefin rings.

[0016] R 3 R 4 and R 5 Selected from the following groups: hydrogen, C1-C4-alkyl, unsubstituted or substituted with C1-C4-alkyl and / or halogen (especially chlorine or fluorine) C6-C 10 -aryl (especially phenyl substituted with C1-C4-alkyl) and SiR3, OR, NR2, SR, PR2, where R represents C1-C4-alkyl, respectively. 10 -alkyl, C5-C 10 -Cycloalkyl and unsubstituted or C1-C 10 -alkyl or C1-C4-dialkylamino substituted C6-C 10 -aryl, especially phenyl substituted with C1-C4-alkyl, thereby preferably R 3 R 4 and R 5 Selected from the following groups: hydrogen, C1-C4-alkyl, unsubstituted or substituted with C1-C4-alkyl and / or halogen (especially chlorine or fluorine) C6-C 10 -aryl, especially phenyl substituted with C1-C4-alkyl, more preferably with R group 3 To R 5 At least one of them means a C1-C4 alkyl group, especially a methyl group, and

[0017] L is the amidine ligand of formula (3).

[0018]

[0019] The amidine ligand is covalently bonded to the metal M via an imine nitrogen atom, and

[0020] Sub1 is an unsubstituted or C6-C1 substituted C1-C4 alkyl and / or halogenated, especially chlorine or fluorine substituted C6-C4 alkyl. 10 -Aromatic substituents, especially phenyl groups and

[0021] Sub2 is a substituent containing a Group 15 heteroatom, through which Sub2 bonds to the imine carbon atom or

[0022] Sub1 and Sub2, together with the imino groups they are attached to, form ligands of formula (3a).

[0023]

[0024] The amidine-containing ligand (3a) is via an imine nitrogen atom N 2 Covalently bonded to metal M,

[0025] The benzo[a]ring fused with the amidine ring can be unsubstituted or contain additional substituents R. 7 These substituents each have an index "q", selected from the group consisting of hydrogen, C1-C4-alkyl, and halogen, and thus q is a number from 0 to 4, preferably from 0 to 2, and most preferably 0.

[0026] Sub4 is an aliphatic or aromatic cyclic or linear substituent containing a Group 14 atom, through which Sub4 interacts with the amino nitrogen atom N. 1 Bonding, preferably Sub4 is C6-C 10 The aromatic ring, preferably phenyl, is either unsubstituted or substituted with one or more substituents selected from the group consisting of halogens, especially Cl or F and C1-C4-alkyl groups.

[0027] R 1 and R 2

[0028] In a preferred embodiment, R 1 and R 2 Selected from the following groups respectively: hydrogen, C1-C 10 -alkyl, C5-C 10 -Cycloalkyl and unsubstituted or C1-C 10 -alkyl-substituted C6-C 10 -aryl, especially phenyl substituted with C1-C4-alkyl, or R 1 and R 2Together with the two double-bonded carbon atoms of the thiophene ring to which they are attached, they form unsubstituted or C1-C4-alkyl-substituted aliphatic C5-C6-cyclic olefin rings.

[0029] M

[0030] In a preferred embodiment, the group 4 metal M is titanium (Ti), zirconium (Zr), or hafnium (Hf), with titanium being the most preferred.

[0031] TCy

[0032] As used herein, the term cyclopentadienyl ligand is intended to convey its conventional meaning broadly, namely, a substituted ligand having a five-membered carbon ring that bonds to a metal via π-type bonding, typically in an η-type relationship with the metal. 5 -Coordination.

[0033] Preferably, the substituent R of the TCy ligand 3 R 4 and R 5 They should respectively have the following meanings: hydrogen, C1-C4-alkyl (especially methyl and isopropyl), phenyl, fluorophenyl, and halogen. In a preferred embodiment, R 3 To R 5 All should be selected from groups consisting of free hydrogen, methyl, and isopropyl groups.

[0034] Also preferred are metal complexes of formula (1), wherein TCy is a thiophene-fused cyclopentadienyl ligand of formula (2a).

[0035]

[0036] in

[0037] n is a number between 3 and 4, and

[0038] R 6 For each index m, it refers to C1-C4-alkyl.

[0039] m is a number from 0 to 4, preferably from 0 to 2, and R 3 R 4 and R 5 It has the meanings given above.

[0040] Any R 6 Substituents will replace the hydrogen in the corresponding CH2 unit fused to the thiophene ring.

[0041] Z

[0042] In a preferred embodiment, Z independently refers to a halogen atom, C 1-10 Alkyl, C7-20 Aryl alkyl, C 6-20 Aryl or C 1-20 Hydrocarbon-substituted amino groups, C 1-20 Alkoxy groups, and more preferably, halogen atoms and C 1-10 Alkyl, C 7-20 Aryl groups, most preferably Cl, methyl, benzyl, or methyltrimethylsilyl. Cl or methyl are most preferred. If p is greater than 1, meaning p = 2, then the given meaning of Z is independent. Preferably, p = 2 and both Z are the same.

[0043] L

[0044] Typical examples of such preferred amidoyl ligands are represented by Formula 3, wherein Sub1 is a phenyl or substituted phenyl residue, preferably 2,6-dimethylphenyl, 2,6-dichlorophenyl or 2,6-difluorophenyl.

[0045] Another preferred embodiment of the invention relates to a metal complex of formula (1) having L of formula (2), wherein Sub2 has the general formula -NR 8 R 9 , where R 8 and R 9 The residues are selected from the following groups: aliphatic hydrocarbon groups, halogenated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and halogenated aromatic hydrocarbon groups. R 8 Optional with R 9 Or Sub1 forms a heterocyclic structure. Examples of Sub2 are diformamide, diisopropylamide, and bicyclohexylamide. The most preferred example of an amidine-containing ligand represented by formula (3) is based on proton-midine of formula (3H).

[0046]

[0047] Examples include N,N-dimethylacetamidine, N,N-diisopropylacetamidine, N,N-dicyclohexylacetamidine, N-(2,6-dimethylphenyl)-N-ethylacetamidine, N,N-dimethylisobutylamidine, N,N-diisopropylisobutylamidine, N,N-dicyclohexylisobutylamidine, N-(2,6-dimethylphenyl)-N-ethylisobutylamidine, and N,N-dimethyl-cyclohexylacetamidine. Methanemidine, N,N-diisopropylcyclohexanemidine, N,N-dicyclohexylcyclohexanemidine, N-(2,6-dimethylphenyl)-N-ethylcyclohexanemidine, N,N-dimethylneopramidine, N,N-diisopropylneopramidine, N,N-dicyclohexylneopramidine, N-(2,6-dimethylphenyl)-N-ethylneopramidine, 2,2,2-trifluoro-N, N-Dimethylacetamidine, 2,2,2-trifluoro-N,N-diisopropylacetamidine, N,N-dicyclohexyl-2,2,2-trifluoroacetamidine, N-(2,6-dimethylphenyl)-N-ethyl-2,2,2-trifluoroacetamidine, 2-(phenyl)-N,N-dimethylacetamidine, 2-(phenyl)-N,N-diisopropylacetamidine, N,N-dicyclohexyl- 2-(phenyl)acetamidine, 2-(phenyl)-N-(2,6-dimethylphenyl)-N-ethylacetamidine, 2-(2,6-dimethylphenyl)-N,N-dimethylacetamidine, 2-(2,6-dimethylphenyl)-N,N-diisopropylacetamidine, N,N-dicyclohexyl-2-(2,6-dimethylphenyl)acetamidine, N,2-bis(2,6-dimethylphenyl)acetamidine 2-(2,6-difluorophenyl)-N,N-dimethylacetamidine, 2-(2,6-difluorophenyl)-N,N-diisopropylacetamidine, N,N-dicyclohexyl-2-(2,6-difluorophenyl)acetamidine, 2-(2,6-difluorophenyl)-N-(2,6-dimethylphenyl)-N-ethyl-acetamidine, N,N-dimethyl- Benzamide, N,N-diisopropylbenzamide, N,N-dicyclohexylbenzamide, N-(2,6-dimethylphenyl)-N-ethylbenzamide, N,N-dimethyl-1-naphthamide, N,N-diisopropyl-1-naphthamide, N,N-dicyclohexyl-1-naphthamide, N-(2,6-dimethylphenyl)-N-ethyl-1-naphthamide, N,N,2,6 -Tetramethylbenzamide, N,N-diisopropyl-2,6-dimethylbenzamide, N,N-dicyclohexyl-2,6-dimethylbenzamide, N-(2,6-dimethylphenyl)-N-ethyl-2,6-dimethylbenzamide, 2,6-difluoro-N,N-dimethylbenzamide, 2,6-difluoro-N,N-diisopropylbenzamide, N,N-dicyclohexyl- 2,6-Difluorobenzoamidine, N-(2,6-dimethylphenyl)-N-ethyl-2,6-difluorobenzoamidine, 2,6-dichloro-N,N-dimethylbenzoamidine, 2,6-dichloro-N,N-diisopropylbenzoamidine, 2,6-dichloro-N,N-dicyclohexylbenzoamidine, 2,6-dichloro-N-(2,6-dimethylphenyl)-N-ethyl-benzoamidine.Preferred examples are 2,6-difluoro-N,N-piperidinylbenzamidinium, 2,4-difluoro-N,N-diisopropylbenzamidinium (2,4-difluoro-N,N-diisopropylbenzamidinium), 2,4,6-trifluoro-N,N-diisopropylbenzamidinium (2,4,6-trifluoro-N,N-diisopropylbenzamidinium), and 3,5-difluoro-N,N-diisopropylbenzamidinium. Propylbenzamide (3,5-difluoro-N,N-diisopropylbenzamide), pentafluoro-N,N-diisopropylbenzamide (pentafluoro-N,N-diisopropylbenzamide), 2,6-difluoro-N,N-diisopropylbenzamide (2,6-difluoro-N,N-diisopropylbenzamide), and N,N-diisopropylbenzamide (N,N-diisopropylbenzamide).

[0048] Another preferred embodiment of the invention relates to a metal complex of formula (1) having a ligand L of formula (3a).

[0049]

[0050] The amidine-containing ligand (3a) is via an imine nitrogen atom N 2 Covalently bonded to metal M,

[0051] The benzo[a]ring fused with the amidine ring can be unsubstituted or contain additional substituents R. 7 These substituents each have an index "q", selected from the group consisting of hydrogen, C1-C4-alkyl, and halogen, and thus q is a number from 0 to 4, preferably from 0 to 2, and most preferably 0.

[0052] Sub4 is an aliphatic or aromatic cyclic or linear substituent containing a Group 14 atom, through which Sub4 interacts with the amino nitrogen atom N. 1 Bonding, preferably Sub4 is C6-C 10 The aromatic ring, preferably phenyl, is either unsubstituted or substituted with one or more substituents selected from the group consisting of halogens, especially Cl or F, and C1-C4-alkyl groups, especially methyl groups.

[0053] Preferred R 7 Typical examples are hydrogen and fluorine.

[0054] The preferred metal complex is that of formula (1), wherein

[0055] M is Ti,

[0056] Z is selected from chlorine, C1-C4-alkyl, and C 7-20 The group consisting of aralkyl groups, preferably methyl or benzyl.

[0057] p is 2

[0058] TCy is a ligand of formula (2), wherein R1 and R2 are independent of another hydrogen, methyl, phenyl, or C1-C4-alkyl-substituted phenyl group.

[0059] R 3 R 4 and R 5 Independent of another hydrogen, methyl, fluorophenyl, isopropylphenyl, or

[0060] TCy is the ligand of equation (2a), where m = 0.

[0061] method

[0062] The present invention also relates to a method for manufacturing a metal complex of formula (1), wherein the metal complex of formula (3) is made

[0063] TCyMZ p+1 (3)

[0064] Reaction with amidine of formula LH or its hydrohalate LH·HZ, wherein L has the meaning of at least one of claims 1 to 6, and Z means halogen, aralkyl or alkoxy, especially Cl, benzyl or isopropyl.

[0065] The reaction with LH or its hydrohalate LH·HZ is preferably carried out in a suitable solvent and, more preferably, in the presence of a suitable base.

[0066] Suitable bases include organic bases, inorganic bases, and organometallic compounds. Typical examples of suitable bases are triethylamine and methylmagnesium bromide / methylmagnesium chloride.

[0067] A suitable solvent is preferably an aromatic or aliphatic hydrocarbon solvent. The reaction is preferably carried out under ambient pressure, more preferably at 0.9 bar to 1.1 bar, and at a temperature in the range of 0 to 90°C. More preferably, in the range of 20°C to 60°C.

[0068] LH or LH·HZ and TCYMZ p+1 The molar ratio is preferably in the range of 0.8 to 1.5, and most preferably in the range of 0.95 to 1.05. The suitable molar ratio of alkali to LH and LH·HZ is preferably in the range of 1 to 5, and more preferably in the range of 2 to 4.

[0069] The metal complex of formula (1), in which Z refers to a halogen atom, can be separated by means of filtration to remove any inorganic or organic salt byproducts, followed by depressurization to remove volatiles or by crystallization followed by filtration or decantation to remove the mother liquor. Optionally, the crude mixture can be used in the polymerization reaction without further post-treatment or purification steps.

[0070] Techniques well known to those skilled in the art are used to further obtain a metal complex of formula (1) from a metal complex of formula (1) (where Z signifies a halogen atom) by using a suitable alkylating agent, preferably in a suitable solvent, via a salt metathesis reaction, where Z signifies C1-10 alkyl, C7-20 aralkyl, or C6-20 aryl. Preferably, a Grignard reagent or an organolithium reagent is used as the alkylating agent. The molar ratio of the alkylating agent, especially the alkylating agent, to the metal complex of formula (1) is preferably in the range of 1.8 to 5.0, more preferably in the range of 2.0 to 2.5. The alkylating agent is preferably methylmagnesium chloride, methyllithium, benzylmagnesium chloride, or benzylmagnesium bromide. This can be carried out at ambient pressure, preferably at 0.9 bar to 1.1 bar, and at a temperature in the range of 0 to 90°C. Preferably in the range of -30°C to 30°C.

[0071] Alternatively, LH or LH·HZ can be combined with TCyMZ. p+1 (where Z refers to C1-10 alkyl, C7-20 aralkyl, C6-20 aryl, and A, p, and n have the meanings mentioned above) are combined in a suitable solvent to prepare the metal complex of formula (1) (where Z refers to C1-10 alkyl, C7-20 aralkyl, C6-20 aryl, and A, p, and n have the meanings mentioned above) 7-20 Aryl alkyl, C6-20 aryl). A suitable solvent is preferably an aromatic or aliphatic hydrocarbon solvent. This can be carried out at ambient pressure, preferably at 0.9 bar to 1.1 bar, and preferably at a temperature in the range of 0 to 120°C. More preferably, in the range of 70°C to 110°C.

[0072] The present invention further provides a catalyst system comprising...

[0073] a) Metal complex according to formula (1) of the present invention

[0074] and

[0075] b) Activator and

[0076] c) Optional cleaning agent.

[0077] The preferred metal complex of compound a) was mentioned above. Scavenger c) is a compound that reacts with impurities present in the method of the present invention, which are toxic to the catalyst.

[0078] In a preferred embodiment of the present invention, the scavenger c) of the catalyst system is a hydrocarbon group of a group 1-13 metal or metalloid, or the reaction product of the catalyst system with at least one sterically hindered compound containing a group 15 or 16 atom.

[0079] Preferably, the group 15 or 16 atom of the sterically hindered compound carries a proton. Examples of such sterically hindered compounds are tert-butanol, isopropanol, triphenylmethanol, 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butylaniline, 4-methyl-2,6-di-tert-butylaniline, 4-ethyl-2,6-di-tert-butylaniline, HMDS (hexamethyldisilazane), diisopropylamine, di-tert-butylamine, diphenylamine, etc. Some non-limiting examples of scavengers are organoaluminum compounds (E), butyllithium (including its isomers), dialkylmagnesium and alkylzinc, and their reaction products with sterically hindered compounds or acids such as HF, HCl, HBr, HI. Furthermore, organoaluminum compounds (E) as defined below can be used as activators b), especially alkylaluminoxanes such as methylaluminoxane (MAO).

[0080] The activator for component b) of the unit site catalyst is well known in the art. These activators often contain group 13 atoms, such as boron or aluminum. Examples of these activators are described in Chem. Rev. [Chemical Review], 2000, 100, 1391, by EY-X. Chen and TJ Marks. Preferred activators b) are boranes (C1), borates (C2, C3) or organoaluminum compounds (E), such as alkylaluminoxanes, such as methylaluminoxane (MAO). The activator used for activation is preferably any boron compound and / or organoaluminum compound (E) from (C1) to (C3). Organoaluminum compounds (E) can be used as scavengers and / or activators.

[0081] (C1) Boron compounds represented by the general formula BQ1Q2Q3

[0082] (C2) Boron compounds represented by the general formula G(BQ1Q2Q3Q4)

[0083] (C3) Boron compounds represented by the general formula (JH)(BQ1Q2Q3Q4)

[0084] Q1 to Q3 are halogen atoms, hydrocarbon groups, haloalkyl groups, substituted silyl groups, alkoxy groups, or disubstituted amino groups, and they may be the same or different. Q1 to Q3 are preferably halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, haloalkyl groups having 1 to 20 carbon atoms, substituted silyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, or amino groups having 2 to 20 carbon atoms, and more preferably Q1 to Q3 are halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, or haloalkyl groups having 1 to 20 carbon atoms. More preferably, Q1 to Q3 are fluorinated hydrocarbon groups having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably, Q1 to Q3 are fluorinated aryl groups having 6 to 20 carbon atoms containing at least one fluorine atom. Q4 has the same meaning as one of the groups Q1 to Q3, and Q1 to Q4 may be the same or different. G is an inorganic or organic cation, J is a neutral Lewis base, and (JH) is a Brønsted acid.

[0085] In boron compounds (C1) represented by the general formula BQ1Q2Q3, B is a trivalent boron atom, and Q1 to Q3 have the meanings mentioned above and may be the same or different.

[0086] Specific examples of compound (C1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenyl-bis(pentafluorophenyl)borane, etc., with tris(pentafluorophenyl)borane being the most preferred.

[0087] In boron compounds (C2) represented by the general formula G(BQ1Q2Q3Q4), G + It is an inorganic or organic cation, B is a trivalent boron atom, and Q1 to Q4 are as defined above for Q1 to Q3 in (C1).

[0088] Specific examples of inorganic cations G in compounds represented by the general formula G (BQ1Q2Q3Q4) include ferrocene cations, alkyl-substituted ferrocene cations, silver cations, etc., and specific examples of organic cations G include triphenylmethyl cations, etc. G is preferably a carbocation, and particularly preferably a triphenylmethyl cation.

[0089] Examples of (B Q1Q2Q3Q4) include tetra(pentafluorophenyl)borate, tetra(2,3,5,6-tetrafluorophenyl)borate, tetra(2,3,4,5-tetrafluorophenyl)borate, tetra(3,4,5-trifluorophenyl)borate, tetra(2,3,4-trifluorophenyl)borate, phenyltri(pentafluorophenyl)borate, tetra(3,5-bis(trifluoromethylphenyl)borate, etc.

[0090] As specific combinations thereof, ferrocene tetra(pentafluorophenyl)borate, 1,1'-dimethylferrocene tetra(pentafluorophenyl)borate, silver tetra(pentafluorophenyl)borate, triphenylmethyl tetra-(pentafluorophenyl)borate, triphenylmethyl-tetra(3,5-bistrifluoromethylphenyl)borate, etc. are listed, with triphenylmethyl tetra(pentafluorophenyl)borate being the most preferred.

[0091] In the general formula (JH) + In the boron compound (C3) represented by (BQ1Q2Q3Q4), J is a neutral Lewis base, (JH) is a Brønsted acid, B is a trivalent boron atom, and Q1 to Q4 are defined as in the Lewis acids (C1) mentioned above.

[0092] Brønsted acid (JH) in compounds represented by the general formula (JH)(BQ1Q2Q3Q4) + Specific examples include trialkyl-substituted ammonium compounds, N,N-dialkylphenylammonium compounds, dialkylammonium compounds, triarylphosphine compounds, etc., and the same compounds as above are listed as (B Q1Q2Q3Q4). Specific combinations thereof include triethylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tri(n-butyl)ammonium-tetra(pentafluorophenyl)borate, tri(n-butyl)ammonium tetra(3,5-bis(trifluoromethyl-phenyl)borate, N,N-dimethylaniline tetra(pentafluorophenyl)borate, N,N-diethylaniline tetra(pentafluorophenyl)borate, N,N-2,4,6-pentamethylaniline-tetra(pentafluorophenyl)borate, N,N-di... Methylaniline tetra(3,5-bis(trifluoromethyl-phenyl)borate, diisopropylammonium tetra(pentafluorophenyl)borate, dicyclohexyl-tetra(pentafluorophenyl)borate, triphenylphosphine tetra(pentafluorophenyl)borate, tri(methylphenyl)phosphine tetrabutyl(pentafluorophenyl)borate, tri(dimethylphenyl)phosphine-tetra(pentafluorophenyl)borate, etc., with tri(n-butyl)ammonium-tetra(pentafluorophenyl)borate or N,N-dimethylaniline tetra(pentafluorophenyl)borate being the most preferred.

[0093] The preferred molar ratio of the metal complex to the activated co-catalyst C1-C3 is 1:10 to 2:0, more preferably 1:5 to 1:0, and most preferably 1:3 to 1:1.

[0094] The organoaluminum compound (E) is an aluminum compound having carbon-aluminum bonds, preferably selected from one or more aluminum compounds from (E1) to (E3).

[0095] (E1) From the general formula T 1 a AlZ 3-a Organoaluminum compounds

[0096] (E2) Cyclic alumoxane having a structure represented by the general formula {-Al(T 2 )-O-} b

[0097] (E3) Linear alumoxane having a structure represented by the general formula T 3 {-Al(T 3 )-O-} c AlT 3 2

[0098] (wherein, each of T 1 , T 2 and T 3 is a hydrocarbyl group, and all T 1 , all T 2 and all T 3 can be the same or different respectively. Z represents a hydrogen atom or a halogen atom, and all Z can be the same or different. 'a' represents a number satisfying 0 < a ≤ 3, 'b' is an integer of 2 or greater, and 'c' is an integer of 1 or greater.).

[0099] The hydrocarbyl group in E1, E2 or E3 is preferably a hydrocarbyl group having 1 to 8 carbon atoms, and more preferably an alkyl group.

[0100] Specific examples of the organoaluminum compound (E1) represented by T 1 a AlZ 3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum and the like; dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride and the like; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride and the like; dialkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride and the like; and so forth.

[0101] A preferred activator-scavenger combination is [CPh3][B(C6F5)4] / MAO.

[0102] Cyclic alumoxane E2 having a structure represented by the general formula {-Al(T 2 )-O-} b and linear alumoxane having a structure represented by the general formula T 3 {-Al(T 3 )-O-} c AlT 3 ​Specific examples of linear aluminum oxanes E3 represented by 2 include alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, neopentyl, etc. b is an integer of 2 or greater, and c is an integer of 1 or greater. Preferably, T 2 and T 3 It indicates methyl or isobutyl, and b is 2 to 40, c is 1 to 40.

[0103] The aforementioned aluminum oxanes are prepared by various methods. These methods are not particularly limited, and aluminum oxanes can be generated according to known methods. For example, an aluminum oxane can be generated by contacting a solution prepared by dissolving at least one trialkylaluminum (e.g., trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) with water.

[0104] The preferred molar ratio of the metal complex (1) to the scavenger (c) is 0.1:1000 to 0.1:10, more preferably 0.1:1000 to 0.1:300, and most preferably 0.14:600 to 0.14:400.

[0105] polymerization

[0106] The present invention also provides a method for polymer polymerization by polymerizing at least one, preferably at least two, olefinic monomers, the method comprising contacting the monomers with a metal complex of formula (1).

[0107] The metal complex of formula (1) can also be used as a supported catalyst, which comprises an organometallic compound of formula (1), a support material, and optionally an activator (b) and / or a scavenger (c).

[0108] The carrier material is defined as an inorganic or organic compound that is insoluble in the inert hydrocarbon solvent in which the method of the present invention is carried out. Suitable inorganic carriers include silica, magnesium halides (such as MgF2, MgCl2, MgBr2, MgI2), zeolites, and alumina. Suitable organic carriers include polymers. Some non-limiting examples of polymer carriers are polyolefins, such as polystyrene, polypropylene, and polyethylene, condensation polymers, such as polyamides and polyesters, and combinations thereof.

[0109] The preferred polymerization method typically involves contacting at least one (preferably at least two) olefinic monomers with a metal complex of formula (1) or a catalyst system according to the invention in the gas phase, slurry, or solution of an inert solvent (preferably a hydrocarbon solvent). A suitable solvent is in the gas phase, slurry, or solution form of an inert solvent (preferably a hydrocarbon solvent). A suitable solvent is C 5-12 Hydrocarbons, such as pentane, hexane, heptane, octane, isomers and mixtures thereof, cyclohexane, methylcyclohexane, pentamethylheptane, and hydrogenated naphtha. The method of the present invention can be carried out at a temperature from 10°C to 250°C, depending on the product prepared.

[0110] Single-unit definition

[0111] Alkene monomers should be understood as molecules containing at least one polymerizable double bond.

[0112] The suitable alkene monomer is C 2-20 Olefins. Preferred monomers include unsubstituted or substituted monomers with at most two C atoms. 1-6 alkyl-substituted ethylene and C 3-12 α-Alkenes, unsubstituted or C-shaped alkenes substituted with at most two substituents 8-12 Vinyl aromatic monomers, these substituents are free C 1-4 alkyl groups and unsubstituted or C-shaped groups 1-4 C with alkyl group substitution 4-12 The group consisting of straight-chain or cyclic hydrocarbon groups. Illustrative and non-limiting examples of such α-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecaene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecaene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. These α-olefins can be used in combination.

[0113] The monomer can also be a polyene containing at least two double bonds. In the chain, ring system, or combination thereof, the double bonds can be conjugated or non-conjugated, and they can be intracyclic and / or excyclic and can have different amounts and types of substituents. This means that the polyene can contain at least one aliphatic, alicyclic, or aromatic group, or a combination thereof.

[0114] Suitable polyenes include aliphatic and alicyclic polyenes. More specifically, aliphatic polyenes may be mentioned, such as 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 1,5-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 4-methyl-1,4-octadiene, and 5-methyl-1,4-octadiene. 4-Ethyl-1,4-octadiene, 5-Ethyl-1,4-octadiene, 5-Methyl-1,5-octadiene, 6-Methyl-1,5-octadiene, 5-Ethyl-1,5-octadiene, 6-Ethyl-1,5-octadiene, 1,6-octadiene, 6-Methyl-1,6-octadiene, 7-Methyl-1,6-octadiene, 6-Ethyl-1,6-octadiene, 6-Propyl-1,6-octadiene, 6-Butyl-1,6-octadiene, 1,7-octadiene, 4-Methyl-1,4-nonadiene, 5-Methyl-1,4-nonadiene, 4-Ethyl-1,4-nonadiene, 5-Ethyl-1,4-nonadiene, 5-Methyl-1 5-Nonadiene, 6-Methyl-1,5-nonadiene, 5-Ethyl-1,5-nonadiene, 6-Ethyl-1,5-nonadiene, 6-Methyl-1,6-nonadiene, 7-Methyl-1,6-nonadiene, 6-Ethyl-1,6-nonadiene, 7-Ethyl-1,6-nonadiene, 7-Methyl-1,7-nonadiene, 8-Methyl-1,7-nonadiene, 7-Ethyl-1,7-nonadiene, 1,8-nonadiene, 5-Methyl-1,4-decadiene, 5-Ethyl-1,4-decadiene, 5-Methyl-1,5-decadiene, 6-Methyl-1,5-decadiene, 5-Ethyl-1,5-decadiene, 6-Ethyl-1,5- Decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 1,9-decadiene, 1,5,9-dectriene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, 1,13-tetradecadiene, 1,3-butadiene, and isoprene.

[0115] Alicyclic polyenes can consist of at least one cyclic segment. Examples of such alicyclic polyenes are vinylcyclohexene, vinylnorbornene, ethylidenenorbornene, dicyclopentadiene, cyclooctadiene, 2,5-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclopentane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, and 1-isopropenyl-3-vinylcyclopentane and 1,4-cyclohexadiene. Preferred polyenes are those having at least one intracyclic double bond and optionally at least one excyclic double bond, such as 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, 5-vinylnorbornene and 2,5-norbornediene, dicyclopentadiene and vinylcyclohexene.

[0116] Examples of aromatic polyenes are divinylbenzene (including its isomers), trivinylbenzene (including its isomers), and vinylisopropenylbenzene (including its isomers).

[0117] All of the monomers mentioned above may be further substituted by at least one group containing heteroatoms of groups 13-17 or combinations thereof.

[0118] Homopolymers, copolymers and copolymers, as well as blends thereof, based on three or more of the olefinic monomers mentioned herein can be prepared using the method of the present invention.

[0119] In a preferred embodiment, copolymers based on the metal complexes of the present invention are prepared using ethylene, at least one C... 3-12 An α-olefin (preferably propylene) and at least one non-conjugated diene, preferably selected from the group consisting of 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornediene, dicyclopentadiene (DCPD), and vinylcyclohexene, and more preferably a diene selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinylnorbornene.

[0120] This invention also relates to polymers obtainable using the metal complexes or catalyst systems of this invention. The invention will now be illustrated by examples and comparative experiments, but is not limited thereto. Detailed Implementation

[0121] Example

[0122] Test method.

[0123] Size exclusion chromatography (SEC-IR) using an infrared (IR) detector:

[0124] Equipment: Freeslate Rapid GPC system

[0125] Single detection (Polymer Char's independent infrared detector IR4)

[0126] Column: PLGel Mixed-B 10μm (x3 300×7.5mm column)

[0127] Calibration: Calibrate according to linear polystyrene (PS) standards.

[0128] (Molecular weight approximately 30-3000 kg / mol)

[0129] Temperature: 140℃

[0130] Flow rate: 1.5 ml / min

[0131] Injection volume: 125 μl

[0132] Solvent / eluent: 1,2,4-trichlorobenzene and 0.4 g / L BHT

[0133] stabilizer

[0134] Sample preparation: Dissolve at approximately 140°C for about 2 hours.

[0135] The sample concentration was 1.5 mg / ml after filtration through a sintered glass filter with a diameter of 2 to 0.5 micrometers.

[0136] NMR measurements were performed on a Bruker Avance 400 spectrometer. 1 (H, 400MHz) spectrum.

[0137] The composition of the copolymer was determined using Fourier transform infrared spectroscopy (FT-IR) according to methods known in the art. FT-IR measurements provide the composition of each monomer as a weight percentage relative to the total composition.

[0138] The composition was determined using mid-frequency FT-IR spectroscopy.

[0139] Part I: Synthesis of Ligands and Compounds

[0140] General principles.

[0141] All operations were performed under argon or nitrogen atmospheres using standard Schlenk line or drying oven techniques. The solvent was degassed by bubbling with nitrogen and then dried by passing it through a suitable desiccant column. Toluene was refluxed over sodium and distilled. The deuterated solvent was dried over potassium (C6D6) or P2O5 (CDCl3 and CD2Cl2), distilled under reduced pressure, and stored under nitrogen in Teflon-valve ampoules. NMR samples were prepared under nitrogen in 5 mm Wilmad 507-PP tubes equipped with J. Young Teflon valves. 1 H and 13 C-{ 1 The H} spectrum was recorded at ambient temperature, with an internal reference to the residual proton solvent ( 1 H) or solvent ( 13 C) Resonance, and reported relative to tetramethylsilane (d = 0 ppm). Chemical shift is expressed as δ (ppm), and coupling constant is expressed as Hz.

[0142] Synthesis of ligands and literature compounds

[0143] 1.1. Ligand synthesis

[0144] 1.1.1. Synthesis of 4,5-dimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one.

[0145]

[0146] At 50℃, 400g of P4O was... 10 A mixture of 33.6 g (400 mmol) thiophene and 40.0 g (400 mmol) tigricyl acid in 50 mL of dichloromethane was added to 280 g of polyphosphoric acid prepared with 85% H3PO4 and stirred for 2.5 hours. The mixture was stirred at this temperature for 2 hours and then poured into 1 L of ice-cold water. The product was extracted with 4 × 300 mL of ethyl acetate. The combined extracts were washed with aqueous Na2CO3 solution, dried over K2CO3, and the solvent was evaporated under vacuum. Fractional distillation of the crude product gave 47.0 g (70%) of a colorless oil that solidified at room temperature and had a boiling point (bp) of 87 °C–90 °C at 2 mbar.

[0147] 1 H NMR (CDCl3, 400MHz): δ7.90-7.91 (d, J=4.8Hz, 1H), 7.05-7.06 (d, J=4.7Hz, 1H), 2.88-2 .94(m,1H),2.53-2.59(m,1H),1.40-1.42(d,J=7.6Hz,3H),1.34-1.36(d,J=7.2Hz,3H).

[0148] 1.1.2. Synthesis of 4,5,6-trimethyl-4H-cyclopentane[b]thiophene

[0149]

[0150] Add 62 mL (180 mmol, 2.87 M ether solution) of MeMgBr to a solution of 3.65 g (27 mmol) of ZnCl2 in 150 mL of THF, followed by 15.0 g (90 mmol) of a solution of 4,5-dimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one in 100 mL of THF. Stir the resulting mixture overnight at 65 °C, then pour it into ice-cold 5% HCl. Separate the organic layer and extract the aqueous layer with 3 × 100 mL of ethyl acetate. Dry the combined extracts on Na2SO4 and evaporate to dryness. Separate the product by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). This procedure yields 13.1 g (88%) of a pale yellow oil.

[0151] 1 H NMR (CDCl3, 400MHz): δ7.08-7.09 (d, J = 4.4Hz, 1H), 7.00-7.01 (d, J = 4.1Hz, 1H), 3.07-3.13 (m, 1H), 2.05 (s, 3H), 1.97 (s, 3H), 1.26-1.28 (d, 3H).

[0152] 1.1.3. Synthesis of 2,4,5-trimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one

[0153]

[0154] At 50℃, 300g of P4O was... 10 A mixture of 29.5 g (300 mmol) of 2-methylthiophene and 30.0 g (300 mmol) of tigricyl acid in 40 mL of dichloromethane was added to 210 g of polyphosphoric acid prepared in 85% H3PO4 for 2.5 hours. The mixture was stirred at this temperature for 2 hours and then poured into 1 L of ice-cold water. The product was extracted with 4 × 200 mL of ethyl acetate. The combined extracts were washed with an aqueous solution of Na2CO3, dried over K2CO3, and the solvent was evaporated under vacuum. Fractional distillation of the crude product gave 44.0 g (82%) of a colorless oil that solidified at room temperature with a boiling point of 119-120 °C / 3 mbar.

[0155] 1H NMR (CDCl3, 400MHz): δ6.71 (s, 1H), 2.76-2.82 (m, 1H), 2.53 (s, 3H), 2.38-2.44 (m, 1H), 1.26-1.33 (m, 6H).

[0156] 1.1.4. Synthesis of 3-bromo-2,4,5-trimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one

[0157]

[0158] A solution of 39.0 g (215 mmol) of 2,4,5-trimethyl-4,5-dihydro-6H-cyclopentane-[b]thiophene-6-one in 100 mL of dichloromethane was added to a suspension of 72.0 g (540 mmol) of AlCl3 in 300 mL of dichloromethane at 0 °C. The resulting suspension was stirred for 10 min, and then 34.6 g (215 mmol) of bromine was added. The reaction mixture was stirred at room temperature for 1 h, then poured into ice-cold water to separate the organic layer, and the aqueous layer was extracted with 3 × 200 mL of dichloromethane. The combined extracts were washed with an aqueous solution of Na₂CO₃, dried over Na₂SO₄, passed through a silica gel 60 pad (40–63 μm), and then evaporated to dryness. Fractional distillation of the residue gave 50.7 g (90%) of a pale yellow oil that solidified at room temperature with a boiling point of 135–137 °C / 2 mbar.

[0159] 1 H NMR (CDCl3, 400MHz): δ2.81-2.86 (m, 1H), 2.47 (s, 3H), 1.28-1.44 (m, 6H).

[0160] 1.1.5. Synthesis of 3-bromo-2,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene

[0161]

[0162] 120 mL (320 mmol, 2.87 M ether solution) of MeMgBr was added to 42.0 g (160 mmol) of 3-bromo-2,4,5-trimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one in 400 mL of THF. The resulting mixture was stirred overnight at 65 °C and then poured into ice-cold 5% HCl. The organic phase was separated, and the aqueous layer was extracted with 3 × 200 mL of ethyl acetate. The combined extracts were dried over Na2SO4 and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). This procedure yielded 40.5 g (97%) of a brown oil.

[0163] 1H NMR (CDCl3, 400MHz): δ3.05-3.10 (m, 1H), 2.40 (s, 3H), 1.94 (s, 3H), 1.91 (s, 3H), 1.29-1.30 (d, J = 7.0Hz, 3H).

[0164] 1.1.6. Synthesis of 2,3,4,5,6-pentamethyl-4H-cyclopentane[b]thiophene

[0165]

[0166] To 15.0 g (57 mmol) of a solution of 3-bromo-2,4,5,6-tetramethyl-4,6a-dihydro-3aH-cyclopentane[b]thiophene in 300 mL of THF, add 600 mg (1.2 mmol) of Pd[P(tBu)3]2 and 24 mL (64 mmol, 2.70 M ether solution) of MeMgBr. The resulting mixture was stirred overnight at 60 °C, poured into water, the organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined extracts were dried over Na2SO4 and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). The yield was 10.3 g (93%) of the product as a pale yellow oil. 1 H NMR (CDCl3, 400MHz): δ3.01-3.07 (m, 1H), 2.40 (s, 3H), 2.17 (s, 3H), 1.99 (s, 3H), 1.94 (s, 3H), 1.25-1.27 (d, J = 7.4Hz, 3H).

[0167] 1.1.7. Synthesis of 2-trimethyl(2,3,4,5,6-pentamethyl-6H-cyclopentathiophen-6-yl)silane

[0168]

[0169] To a solution of 3.2 g (16.6 mmol) of 2,3,4,5,6-pentamethyl-4H-cyclopentane[b]thiophene in 50 mL of THF, 6.7 mL (16.6 mmol, 2.5 M hexane solution) of n-butyllithium was added. The resulting mixture was stirred at this temperature for 1 hour, cooled to -78 °C, and 2.3 mL (18.3 mmol) of trichlorosilane was added. The resulting mixture was warmed to room temperature and then poured into 20 mL of water. The organic phase was separated, and the aqueous layer was extracted with 3 × 30 mL of ethyl acetate. The combined organic extracts were dried over Na₂SO₄ and then evaporated to dryness. This procedure yielded 4.20 g (95%) of a pale yellow oil.

[0170] 1 H NMR (CDCl3, 400MHz): δ2.39(s,3H), 2.28(s,3H), 2.15(s,3H), 1.93(s,3H), 1.37(s,3H), -0.08(s,9H).

[0171] 1.1.8. Synthesis of 1,2,3-trimethyl-1H-benzo[b]cyclopentane[d]thiophene

[0172]

[0173] A mixture of 20 g (150 mmol) benzothiophene and 15.8 g (160 mmol) tic acid was added dropwise to Eaton's reagent, prepared from 16 g P4O10 and 180 ml methanesulfonic acid, while stirring vigorously at 65 °C. The mixture was stirred at this temperature for 1 hour and then poured into ice-cold water. The crude product was extracted with a mixture of hexane and dichloromethane (70:30 volume). The combined extracts were washed with an aqueous solution of Na2CO3, dried over K2CO3, and then evaporated to dryness. The crude product was distilled using a Kugelrohr apparatus (140 °C, 1 mbar) to give 15.0 g of a mixture of 2,3-dimethyl-2,3-dihydro-1H-benzo[b]cyclopent[d]thiophene-1-one and 1,2-dimethyl-1,2-dihydro-3H-benzo[b]cyclopent[d]thiophene-3-one. The mixture was ready for further use without further purification. 52.0 mL (140 mmol, 2.70 M ether solution) of MeMgBr was added to 15.0 g (70 mmol) of dimethyl-dihydro-H-benzo[b]cyclopentyl[d]thiopheneone in 250 mL THF. The resulting mixture was stirred overnight at 65 °C and then poured into ice-cold 5% HCl. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL ethyl acetate. The combined extracts were dried over Na₂SO₄ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). This procedure yielded 11.8 g (37% in two stages) of the title substance as a pale yellow oil.

[0174] 1 H NMR(CDCl3,400MHz): δ7.96-7.98(m,1H),7.84-7.86(m,1H),7.24-7.38(m,2 H), 3.30-3.35 (m, 1H), 2.32 (s, 3H), 2.00 (s, 3H), 1.33-1.35 (d, J = 7.1Hz, 3H).

[0175] 1.1.9. Synthesis of trimethyl(1,2,3-trimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)silane.

[0176]

[0177] To a solution of 11.2 g (52 mmol) of 1,2,3-trimethyl-1H-benzo[b]cyclopentyl[d]thiophene in 250 mL of THF, 20.9 mL (52 mmol, 2.5 M hexane solution) was added. The resulting mixture was stirred at this temperature for 1 hour, cooled to -78 °C, and 7.4 mL (58 mmol) of trichlorosilane was added. The resulting mixture was warmed to room temperature and then poured into 100 mL of water. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined organic extracts were dried over Na₂SO₄ and then evaporated to dryness. This procedure yielded 14.8 g (99%) of a colorless oil.

[0178] 1H NMR(CDCl3,400MHz): δ7.95-7.97(m,1H),7.69-7.71(m,1H),7.31-7.35(m,1 H),7.13-7.17(m,1H),2.11(s,3H),2.02(s,3H),1.62(s,3H),-0.11(s,9H).

[0179] 1.1.10. Synthesis of 3-bromo-4,5-dimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one.

[0180]

[0181] A solution of 20.0 g (120 mmol) of 4,5-dimethyl-4,5-dihydro-6H-cyclopentathiophene-6-one in 40 mL of dichloromethane was added to a suspension of 35.8 g (270 mmol) of AlCl3 in 45 mL of dichloromethane at 0 °C. The resulting suspension was stirred for 10 min, and then 20.6 g (135 mmol) of bromine was added. The reaction mixture was stirred at room temperature for 1 h, then poured into ice-cold water to separate the organic layer, and the aqueous layer was extracted with 3 × 100 mL of dichloromethane. The combined extracts were washed with an aqueous solution of Na₂CO₃, dried over Na₂SO₄, passed through a silica gel 60 pad (40–63 μm), and then evaporated to dryness. This procedure yielded 31.8 g (99%) of a pale yellow solid.

[0182] 1H NMR (CDCl3, 400MHz): δ7.76 (s, 1H), 2.86-2.92 (m, 1H), 2.53-2.59 (m, 1H), 1.31-1.48 (m, 6H).

[0183] 1.1.11. Synthesis of 3-bromo-4,5,6-trimethyl-4H-cyclopentane[b]thiophene

[0184]

[0185] To a solution of 24.8 g (100 mmol) of 3-bromo-4,5-dimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one in 250 mL of THF, 75 mL of MeMgBr (200 mmol, 2.87 M ether solution) was added. The resulting mixture was stirred overnight at 65 °C and then poured into ice-cold 5% HCl. The organic phase was separated, and the aqueous layer was extracted with 3 × 150 mL of ethyl acetate. The combined extracts were dried over Na₂SO₄ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). This procedure yielded 21.5 g (87%) of a pale yellow oil.

[0186] 1 H NMR (CDCl3, 400MHz): δ6.92 (s, 1H), 3.07-3.13 (m, 1H), 1.97 (s, 3H), 1.93 (s, 3H), 1.30-1.32 (d, J = 7.6Hz, 3H).

[0187] 1.1.12. Synthesis of 3,4,5-trimethyl-4H-cyclopentane[b]thiophene-6(5H)-one

[0188]

[0189] At -80°C, 132 mL (321 mmol) of a 2.43 M n-BuLi hexane solution was slowly added to a solution of 45.3 g (321 mmol) of 2,2,6,6-tetramethylpiperidine in 1000 mL of THF. The resulting solution was stirred at this temperature for 2 hours, and then 30.0 g (305 mmol) of 3-methylthiophene was added dropwise while maintaining the temperature below -75°C and stirred at this temperature for 1 hour. Then, 45.7 g (335 mmol) of dry ZnCl2 was added. The resulting suspension was stirred overnight at room temperature, cooled to -30°C, and then 2.0 g (1.7 mmol) of Pd(PPh3)4 and 79.5 g (671 mmol) of crotonyl chloride were added. The reaction mixture was stirred at room temperature for 3 hours, poured into 1000 mL of water, and diluted with 300 mL of diethyl ether. The organic phase was separated, and the aqueous layer was extracted with 3 × 200 mL of diethyl ether. The combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The crude ketene was immediately poured into a solution prepared in advance with 1000 ml of phosphoric acid and 300 g of P4O4. 10 In the preparation of polyphosphoric acid, the reaction mixture was stirred at 80°C for 2 hours and then poured into ice-cold water. The crude product was extracted with a mixture of hexane and dichloromethane (70:30 v / v). The combined extracts were washed with an aqueous solution of Na₂CO₃, dried over K₂CO₃, and then evaporated to dryness. The product was distilled using a Kugelrohr apparatus (90°C / 1 mbar). Yield: 44.0 g (80%) of colorless oil.

[0190] 1 H NMR (CDCl3, 400MHz): δ7.46 (s, 1H), 2.81-2.87 (dq, 1H, J=6.9Hz, J=2.4Hz), 2.46-2.53 (dq, 1H, J = 7.5Hz, J = 2.4Hz), 2.24 (s, 3H), 1.38 (d, 3H, J = 6.9Hz), 1.31 (d, 3H, J = 7.5Hz).

[0191] 1.1.13. Synthesis of 2-bromo-3,4,5-trimethyl-4H-cyclopentane[b]thiophene-6(5H)-one

[0192]

[0193] 46.4 g (260 mmol) of N-bromosuccinimide was added fractionally to a solution of 42.7 g (238 mmol) of 3,4,5-trimethyl-4H-cyclopentathiophene-6(5H)-one in 500 mL of DMF. The reaction mixture was stirred overnight, poured into 1000 mL of water, and then diluted with 300 mL of diethyl ether. The organic phase was extracted with 6 × 150 mL of water. The organic extract was dried over Na₂SO₄ and then evaporated to dryness. This procedure yielded 46.0 g (75%) of a yellow oil.

[0194] 1 H NMR (CDCl3, 400MHz): δ2.82-2.87 (m, 1H), 2.38-2.44 (m, 1H), 2.19 (s, 3H), 1.37 (s, 3H, J = 7.1Hz), 1.29 (d, 3H, J = 7.5Hz).

[0195] 1.1.14. Synthesis of 2-bromo-3,4,5-trimethyl-4H-cyclopentane[b]thiophene-6(5H)-one

[0196]

[0197] To 46.0 g (178 mmol) of 2-bromo-3,4,5-trimethyl-4H-cyclopentathiophene-6(5H)-one in 500 mL of diethyl ether, add 100 mL (266 mmol) of 2.7 M MeMgBr in diethyl ether. The resulting mixture is stirred overnight under reflux and then poured into ice-cold 5% HCl. The organic phase is separated, and the aqueous layer is extracted with 3 × 150 mL of ethyl acetate. The combined organic extracts are dried over Na₂SO₄ and then evaporated to dryness. The residue is purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). This procedure yields 25.0 g (55%) of a yellow oil.

[0198] 1 H NMR (CDCl3, 400MHz): δ3.03-3.08 (m, 1H), 2.19 (s, 3H), 1.95 (s, 3H), 1.90 (s, 3H), 1.24 (d, 3H, J = 7.9Hz).

[0199] 1.1.15. Synthesis of 3,4,5,6-tetramethyl-2-phenyl-4H-cyclopentane[b]thiophene

[0200]

[0201] To a solution of 6.00 g (23.0 mmol) of 2-bromo-3,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene in 150 mL of THF, add 12.0 mL (1.20 mmol) of 0.1 M Pd (P t A toluene solution of Bu3)2 and 20.0 mL (51.0 mmol) of 2.60 M PhMgBr in diethyl ether were used. The resulting mixture was stirred overnight at 60 °C and then poured into water. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined extracts were dried over Na2SO4 and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane). Yield: 4.21 g (71%) of yellow oil.

[0202] 1 H NMR (CDCl3, 400MHz): δ7.37-7.47(m,4H),7.25-7.28(m,1H),3.08-3.14(m,1H),2.35(s,3H),2.02(s,3H),1.96(s,3H),1.30(d,3H,J=7.6Hz).

[0203] 1.1.16. Synthesis of 2-(3,5-di-tert-butylphenyl)-3,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene

[0204]

[0205] To a solution of 5.00 g (19.4 mmol) of 2-bromo-3,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene in 150 mL of THF, add 10.0 mL (1.00 mmol) of 0.1 M Pd (P t A toluene solution of Bu3)2 and 80.0 mL (43.0 mmol) of 0.55 M 3,5-di-tert-butylphenyl magnesium bromide in THF were prepared. The resulting mixture was stirred overnight at 60 °C and then poured into cold water. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined extracts were dried over Na2SO4 and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane). Yield: 5.53 g (78%) of yellow oil.

[0206] 1H NMR (CDCl3, 400MHz): δ7.33(s,1H),7.29(s,2H),3.09-3.12(m,1H),2.34(s,3H),2.01(s,3H),1.95(s,3H),1.33-1.35(m,21H).

[0207] 1.1.17. Synthesis of 2-(2-isopropylphenyl)-3,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene

[0208]

[0209] To a solution of 5.00 g (19.4 mmol) of 2-bromo-3,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene in 150 mL of THF, add 10.0 mL (1.00 mmol) of 0.1 M Pd (P t A toluene solution of Bu3)2 and 80.0 mL (43.0 mmol) of 0.55 M 2-isopropylphenyl magnesium bromide in THF were used. The resulting mixture was stirred overnight at 60 °C and then poured into water. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined extracts were dried over Na2SO4 and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane). Yield: 4.22 g (72%) of yellow oil.

[0210] 1 H NMR (CDCl3, 400MHz): δ7.35-7.40(m,2H),7.27-7.29(m,1H),7.18-7.22(m,1H),3.09-3.17(m,2H),2.0 5(s,3H),2.04(s,3H),1.98(s,3H),1.32(d,3H,J=7.4Hz),1.18(d,3H,J=6.9Hz),1.17(d,3H,J=6.9Hz).

[0211] 1.1.18. Synthesis of 2-cyclohexyl-3,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene

[0212]

[0213] To a solution of 4.10 g (16.0 mmol) of 2-bromo-3,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene in 150 mL of THF, add 8.00 mL (0.80 mmol) of 0.1 M Pd (P tA toluene solution of Bu3)2 and 60.0 mL (48.0 mmol) of 0.8 M cyclohexylmagnesium chloride in diethyl ether were used. The resulting mixture was stirred overnight at 60 °C and then poured into water. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined extracts were dried over Na2SO4 and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane). Yield: 2.51 g (60%) of yellow oil.

[0214] 1 H NMR (CDCl3, 400MHz): δ2.99-3.05(m,1H),2.80-2.86(m,1H),2.18(s,3H),1.96(s,3H),1.91(s,3H),1.89-1. 93(m,2H),1.82-1.84(m,2H),1.72-1.74(m,1H),1.37-1.43(m,4H),1.21-1.30(m,1H),1.24(d,3H,J=7.6Hz).

[0215] 1.1.19. Synthesis of 2,2,5,6,7-pentamethyl-1,2,3,7-tetrahydrodicyclopentane[b,d]thiophene

[0216]

[0217] While stirring vigorously at 65℃, mix 25g of P4O 10 To a solution of Eaton reagent prepared with 130 ml of methanesulfonic acid, add dropwise a mixture of 4.00 g (26.0 mmol) of 5,5-dimethyl-5,6-dihydro-4H-cyclopentane-[b]thiophene and 2.60 g (26.0 mmol) of picric acid. Stir the mixture at this temperature for 2 hours, then pour it into ice-cold water. Extract the crude product with a mixture of hexane and dichloromethane (70:30 v / v). Wash the combined extracts with an aqueous solution of Na₂CO₃, dry them in K₂CO₃, and evaporate to dryness. Distill the crude product using a Kugelrohr apparatus (140 °C / 1 mbar). Add 10 ml (27.0 mmol) of a 2.7 M MeMgBr solution in diethyl ether to a solution of 4.20 g of the crude product in 100 ml of diethyl ether. Stir the resulting mixture under reflux overnight, then pour it into ice-cold 5% HCl. Separate the organic phase and extract the aqueous layer with 3 × 30 ml of ethyl acetate. The combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane). This procedure yielded 2.83 g (67%) of a yellow oil.

[0218] 1H NMR (CDCl3, 400MHz): δ2.95-3.01(m,1H),2.72(m,2H),2.53-2.54(m,2H),1.95(s,3H),1.90(s,3H),1.17-1.25(m,9H).

[0219] 1.1.20. Synthesis of 1,2,3-trimethyl-5,6,7,8-tetrahydro-1H-benzo[b]cyclopentane[d]thiophene

[0220]

[0221] While stirring vigorously at 65℃, mix 50g of P4O 10 To a solution of Eaton reagent prepared with 300 ml of methanesulfonic acid, add dropwise 10.4 g (75.0 mmol) of a mixture of 4,5,6,7-tetrahydrobenzo[b]thiophene and 7.50 g (75.0 mmol) of picric acid. Stir the mixture at this temperature for 2 hours, then pour it into ice-cold water. Extract the crude product with a mixture of hexane and dichloromethane (70:30 v / v). Wash the combined extracts with an aqueous solution of Na₂CO₃, dry with K₂CO₃, and evaporate to dryness. Distill the crude product using a Kugelrohr apparatus (140 °C / 1 mbar). Add 19 ml (49.0 mmol) of a 2.7 M MeMgBr solution in diethyl ether to a solution of 7.22 g of the crude product in 100 ml of diethyl ether. Stir the resulting mixture under reflux overnight, then pour it into ice-cold 5% HCl. Separate the organic phase and extract the aqueous layer with 3 × 70 ml ethyl acetate. The combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residue was purified by rapid chromatography on silica gel 60 (40-63 μm, eluent: hexane). This procedure yielded 6.12 g (87%) of a yellow oil.

[0222] 1 H NMR (CDCl3, 400MHz): δ2.99-3.03(m,1H),2.73-2.81(m,2H),2.56-2.65(m,2H),1.96(s,3H),1.91(s,3H),1.84-1.89(m,3H),1.21-1.27(m,4H).

[0223] 1.1.21. Synthesis of 3-(2-isopropylphenyl)-2,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene

[0224]

[0225] To a solution of 9.40 g (36.5 mmol) of 3-bromo-2,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene in 150 mL of THF, add 1.20 g (2.4 mmol) of Pd[P(tBu)3]2 and 91.3 mL (43.8 mmol, 0.48 M THF solution) of 2-isopropylphenyl magnesium bromide. The resulting mixture was stirred overnight at 60 °C, cooled to room temperature, and poured into 200 mL of water. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). The yield was 10.4 g (95%) of the product as a yellow, viscous, oily substance.

[0226] 1 H NMR (CDCl3, 400MHz): δ7.32-7.34(m,1H),7.20-7.21(m,2H),7.07-7.09(m,1H),3.34(sept,J=6.9Hz,1H),3.1 1-3.17(m,1H),2.40(s,3H),2.17(s,3H),1.94(s,3H),1.40-1.41(d,J=6.9Hz,6H),1.27-1.29(d,J=7.5Hz,3H)

[0227] 1.1.22. Synthesis of 2,5-dimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one

[0228]

[0229] A mixture of 2-methylthiophene (150 g, 1.53 mol, 1.0 equivalent) and methacrylic acid (159 g, 1.84 mol, 1.2 equivalent) was added dropwise to Eaton reagent (made from 175 g P4O) at 80 °C. 10 Prepared with 1400 ml of methanesulfonic acid for 30 minutes. Stir the reaction mixture for another 5 minutes, then pour it into crushed ice. Extract the mixture with dichloromethane (3 × 300 ml), wash the combined organic extracts with 10% Na2CO3 aqueous solution, dry with anhydrous Na2SO4 and evaporate to dryness. Distill the residue (90 °C, 1 mbar) to give a mixture of title compound A (137 g, 54%) and isomer 2,5-dimethyl-5,6-dihydro-4H-cyclopentyl[b]thiophene-4-one B, in a molar ratio A:B = 10:1.

[0230] 1H NMR (400MHz, CDCl3): δ6.74(s,1H,B),6.69(s,1H,A),3.33(d,1H,J=17.1Hz,J=6.0Hz,B),3.16(dd,1H,J=17.2Hz,J=6.8Hz,A),2.90(quind ,1H,J=7.3Hz,J=2.8Hz,A),2.67(dd,1H,J=17.7Hz,J=2.9Hz,B),2.54(s,3H,A),2.44-2.52(m,1H(A)+H(B)+3H(B)),1.28(d,3H(A)+3H(B)).

[0231] 1.1.23. Synthesis of 3-bromo-2,5-dimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one

[0232]

[0233] N-bromosuccinimide (161 g, 907 mmol, 1.1 equivalents) was added aliquots to a solution of 2,5-dimethyl-4,5-dihydro-6H-cyclopentathiophene-6-one (137 g, 824 mmol, 1.0 equivalents) in 800 mL of DMF at room temperature. The resulting solution was stirred overnight. The reaction mixture was poured into 3 L of water and extracted with dichloromethane (3 × 400 mL). The combined organic extracts were washed thoroughly with water, dried over anhydrous Na₂SO₄, and evaporated to dryness. The resulting solid was recrystallized from hexane to give 76.8 g (38%) of the title compound as a single isomer. The mother liquor was evaporated and the residue was purified by column chromatography on silica gel 60 (40–63 μm) to give 63.1 g (31%) of the title compound as a single isomer. Since the NMR spectra of the two fractions were identical, they were combined (overall yield 69%).

[0234] 1 H NMR (400MHz, CDCl3): δ3.11 (dd, 1H, J = 17.5Hz, J = 6.9Hz), 2.92 (quind, 1H, J = 7.3Hz, J = 2.6Hz), 2.43-2.48 (m, 1H), 2.46 (s, 3H), 1.29 (d, 3H, J = 7.4Hz).

[0235] 1.1.24. Synthesis of 2,3,5-trimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one

[0236]

[0237] Anhydrous THF (600 ml) was added to MeMgBr solution (103 ml, 300 mmol, 1.5 equivalents). ZnCl2 (43.6 g, 320 mmol, 1.6 equivalents) was added fractionally at 0 °C. The resulting mixture was warmed to room temperature and stirred for 1 hour. Anhydrous NMP (200 ml), 3-bromo-2,5-dimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one (49.0 g, 200 mmol, 1.0 equivalents), and Pd (P t A solution of Bu3)2 in toluene (40 mL, 6.00 mmol, 0.03 equivalence) was prepared, and the resulting mixture was stirred overnight at 60 °C. The reaction mixture was then poured into 2 L of water and extracted with diethyl ether (3 × 200 mL). The combined organic extracts were thoroughly washed with water, dried over anhydrous Na2SO4, and evaporated to dryness. The residue was purified using a Kugelrohr apparatus (125 °C / 0.4 mbar) to give 26.9 g (74%) of the title compound as a colorless oil.

[0238] 1 H NMR (400MHz, CDCl3): δ3.05 (dd, 1H, J = 17.2Hz, J = 6.8Hz), 2.86 (quind, 1H, J = 7.3H z,J=2.6Hz),2.36-2.41(m,1H),2.37(s,3H),2.02(s,3H),1.25(d,3H,J=7.5Hz).

[0239] 1.1.25. Synthesis of 2,3,5,6-Tetramethyl-4H-cyclopentane[b]thiophene

[0240]

[0241] To a solution of 4.00 g (22.0 mmol) of 2,3,5-trimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one in 100 mL THF, 13.6 mL of 2.9 M (33.0 mmol) MeMgBr in diethyl ether was added. The resulting mixture was stirred overnight at 65 °C and then accurately poured into ice-cold 5% HCl. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL ethyl acetate. The combined extracts were dried over Na₂SO₄ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). Yield: 3.56 g (91%) of a yellow oil.

[0242] 1H NMR (CDCl3, 400MHz): δ2.98(s,2H), 2.38(s,3H), 2.08(s,3H), 2.02(s,3H), 1.98(s,3H).

[0243] 1.1.26. Synthesis of 2,3,5-trimethyl-6-phenyl-4H-cyclopentane[b]thiophene

[0244]

[0245] To a solution of 4.00 g (22.0 mmol) of 2,3,5-trimethyl-4,5-dihydro-6H-cyclopentathiophene-6-one in 100 mL of THF, 8.9 mL of a 2.5 M (33.0 mmol) phenyllithium in diethyl ether was added. The resulting mixture was stirred overnight at 65 °C and then accurately poured into ice-cold 5% HCl. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined organic extracts were dried over Na₂SO₄ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). Yield: 4.38 g (83%) of a yellow oil.

[0246] 1 H NMR (CDCl3, 400MHz): δ7.51-7.57(m,2H),7.40-7.47(m,2H),7.28-7.34(m,1H),3.21(s,2H),2.39(s,3H),2.24(s,3H),2.13(s,3H).

[0247] 1.1.27. Synthesis of 6-(4-fluorophenyl)-2,3,5-trimethyl-4H-cyclopentane[b]thiophene

[0248]

[0249] To a solution of 4.00 g (22.0 mmol) of 2,3,5-trimethyl-4,5-dihydro-6H-cyclopentathiophene-6-one in 100 mL of THF, 8.9 mL of a 2.5 M (33.0 mmol) solution of 4-fluorophenyl lithium in diethyl ether was added. The resulting mixture was stirred overnight at 65 °C and then accurately poured into ice-cold 5% HCl. The organic phase was separated, and the aqueous layer was extracted with 3 × 100 mL of ethyl acetate. The combined organic extracts were dried over Na₂SO₄ and then evaporated to dryness. The crude product was purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). Yield: 4.83 g (85%) of a yellow oil.

[0250] 1 H NMR (CDCl3, 400MHz): δ7.46-7.55(m,2H),7.07-7.16(m,2H),3.20(s,2H),2.40(s,3H),2.21(s,3H),2.13(s,3H).

[0251] 1.1.28. Synthesis of 6-isopropyl-2,3,5-trimethyl-4H-cyclopentane[b]thiophene

[0252]

[0253] Subsequently, 240 mg (1.80 mmol) of anhydrous ZnCl2 and 3.60 mL of a 1.0 M (3.60 mmol) solution of trimethylsilylmethyl magnesium chloride in diethyl ether were added to 14.2 mL of a solution of 0.93 M (13.0 mmol) isopropyl magnesium chloride in THF. The resulting solution was stirred at room temperature for 30 min, then cooled to 0 °C, and 2.00 g (12.0 mmol) of 2,3,5-trimethyl-4,5-dihydro-6H-cyclopentane[b]thiophene-6-one was added. The reaction mixture was refluxed for 2 h, then poured into 100 mL of saturated NH4Cl, followed by the addition of 10 mL of 5% HCl. The aqueous phase was extracted with 3 × 70 mL of diethyl ether, and the combined organic extracts were dried over Na2SO4 and then evaporated to dryness. The residues were purified by rapid chromatography on silica gel 60 (40–63 μm, eluent: hexane). Yield: 1.38 g (56%) of yellow oil. The obtained substance had a purity of approximately 70%, and the major impurity was found to be 2,3,5-trimethyl-6-(prop-2-alkylene)-5,6-dihydro-4H-cyclopentyl[b]thiophene.

[0254] 1 H NMR (CDCl3, 400MHz): δ2.90-3.01 (m, 3H), 2.36 (s, 3H), 2.07 (s, 3H), 2.02 (s, 3H), 1.21 (d, J = 7.0Hz, 6H).

[0255] 1.2. Synthesis of titanium trichloride complex

[0256] A general procedure for preparing trichloride complexes.

[0257]

[0258] THF (10 ml / mmol) was added to a suitable amount of thiophene-fused cyclopentadiene (TCyH, 1 equivalent) to form a solution. Next, n-butyllithium (1 equivalent, 2.5 M hexane solution) was added in a single addition at -80 °C. The resulting solution was stirred at room temperature for 2 hours, cooled to -80 °C, and then titanium tris(isopropoxy)chloride (1 equivalent) was added. The reaction mixture was stirred overnight at room temperature and then evaporated to dryness. The crude tris(isopropanol) (η) was diluted with anhydrous toluene (10 ml / mmol). 5 -L)titanium(IV), followed by the addition of silicon tetrachloride (5 equivalents). The resulting mixture was stirred overnight at 60°C and then evaporated to dryness. The crude product was dissolved in anhydrous dichloromethane, and the resulting suspension was filtered through a diatomaceous earth 503 pad. The resulting filtrate was evaporated to dryness, and the residue was recrystallized from methylcyclohexane.

[0259] Unless otherwise stated, this procedure will be used in the following synthesis.

[0260] 1.2.1. Synthesis of (η5-2,2,5,6,7-pentamethyl-1,2,3-trihydrodicyclopentane[b,d]thiopheneyl)titanium trichloride

[0261]

[0262] Yield: 70%.

[0263] 1 H NMR (CD2Cl2, 400MHz): δ2.70-2.93(m,4H),2.59(s,3H),2.57(s,3H),2.45(s,3H),1.33(s,3H),1.30(s,3H).

[0264] 1.2.2.(η 5 Synthesis of titanium trichloride (-6,7,8-trimethyl-1,2,3,4-tetrahydrocyclohexano[b]cyclopentan[d]thiopheneyl)

[0265]

[0266] Yield: 31%.

[0267] 1 H NMR (CD2Cl2, 400MHz): δ2.78-3.02(m,4H), 2.64(s,3H), 2.58(s,3H), 2.44(s,3H), 1.88-1.94(m,4H).

[0268] 1.2.3.η 5 Synthesis of 2-phenyl-3,4,5,6-tetramethylcyclopentane[b]thiopheneyl)titanium trichloride

[0269]

[0270] Yield: 73%.

[0271] 1 H NMR (CD2Cl2, 400MHz): δ7.45-7.55(m,5H),2.74(s,3H),2.63(s,3H),2.50(s,3H),2.48(s,3H).

[0272] 1.2.4.{η 5 Synthesis of 2-(3,5-di-tert-butylphenyl)-3,4,5,6-tetramethylcyclopentane[b]thiophene}titanium trichloride

[0273]

[0274] Yield: 54%.

[0275] 1 H NMR (CD2Cl2, 400MHz): δ7.54(m,1H),7.37(m,2H),2.76(s,3H),2.64(s,3H),2.54(s,3H),2.49(s,3H),1.39(s,18H).

[0276] 1.2.5.(η 5 Synthesis of 2-cyclohexyl-3,4,5,6-tetramethylcyclopentane[b]thiopheneyl)titanium trichloride

[0277]

[0278] Yield: 55%.

[0279] 1 H NMR(CD2Cl2,400MHz): δ2.97-3.04(m,1H),2.69(s,3H),2.58(s,3H),2.43(s,3H),2.4 0(s,3H),1.96-2.01(m,2H),1.85-1.88(m,2H),1.75-1.78(m,1H),1.27-1.51(m,5H).

[0280] 1.2.6.{η 5 Synthesis of 2-(2-isopropylphenyl)-3,4,5,6-tetramethylcyclopentane[b]thiophene}titanium trichloride

[0281]

[0282] Yield: 38%.

[0283] 1 H NMR (CD2Cl2, 400MHz): δ7.45-7.46(m,2H),7.24-7.39(m,2H),3.00-3.30(br.s,1 H), 2.72 (s, 3H), 2.62 (br.s, 3H), 2.50 (s, 3H), 2.26 (s, 3H), 1.18 (d, 3H, J = 6.6Hz).

[0284] 1.2.7. Synthesis of trichloro(4,5,6-trimethyl-cyclopentane[b]thiophene)titanium

[0285]

[0286] To a suspension of 5.35 g (134 mmol) of dry potassium hydride in 400 mL of THF, a solution of 21.9 g (134 mmol) of 4,5,6-trimethyl-4H-cyclopentyl[b]thiophene in 100 mL of THF was slowly added. The resulting mixture was stirred at 50 °C for 4 hours and then filtered through a diatomaceous earth mat. The filtrate was evaporated to dryness. The residue was ground with 25 mL of hexane, and the resulting mixture was filtered through a glass frit. The potassium salt thus obtained was washed with 2 × 10 mL of hexane and dried under vacuum. The resulting powder was dissolved in 400 mL of THF, and the resulting solution was cooled to -30 °C while adding a solution of 34.9 g (134 mmol) of tris(isopropoxy)titanium chloride in 100 mL of THF with vigorous stirring. The resulting mixture was stirred overnight at room temperature, filtered through a diatomaceous earth mat, and then evaporated to dryness. The residue was dissolved in 700 mL of toluene, and 101 g (600 mmol) of silicon tetrachloride was added. The resulting mixture was stirred at 60°C for 4 hours and then evaporated to dryness. The residue was dissolved in 700 ml of toluene, and the resulting solution was filtered through a diatomaceous earth mat. The filtrate was evaporated to approximately 50 ml, and 250 ml of hexane was added. The resulting suspension was cooled to -30°C, and the precipitate was collected by filtration through a glass frit. The precipitate was washed with 2 × 100 ml of cold hexane and then dried under vacuum. This procedure yielded 27.8 g (65%) of a dark purple powder.

[0287] 1 H NMR (CDCl3, 400MHz): δ7.71-7.72 (d, J=5.3Hz, 1H), 7.17-7.18 (d, J=5.3Hz, 1H), 2.64 (s, 3H), 2.63 (s, 3H), 2.48 (s, 3H).

[0288] 1.2.8. Synthesis of trichloro(3-(2-isopropylphenyl)-2,4,5,6-trimethylcyclopentane[b]thiophene)titanium

[0289]

[0290] As described for trichloro(4,5,6-trimethyl-cyclopentyl[b]thiophene)titanium, the compound was obtained starting from dry potassium hydride (1.02 g, 25.5 mmol), 3-(2-isopropylphenyl)-2,4,5,6-tetramethyl-4H-cyclopentyl[b]thiophene (7.60 g, 25.5 mmol), 210 ml THF, tris(isopropoxy)titanium chloride (6.63 g, 25.5 mmol), 200 ml toluene, and silicon tetrachloride (19.5 g, 115 mmol). The yield was 6.70 g (49%) of a dark purple product.

[0291] 1 H NMR (CDCl3, 400MHz): δ7.51 (d, J = 7.3Hz, 1H), 7.39-7.48 (m, 2H), 7.26-7.36 (m, 1H), 2.54-2.6 9(m,4H),2.39(s,3H),2.37(s,3H),2.10(s,3H),1.11(d,J=6.9Hz,3H),1.08(d,J=6.9Hz,3H)

[0292] 1.2.9. Synthesis of trichloro(2,3,4,5,6-pentamethylcyclopentane[b]thiophene)titanium

[0293]

[0294] A solution of 3.00 g (16 mmol) of titanium tetrachloride in 20 mL of dichloromethane was added dropwise to a solution of 4.20 g (16 mmol) of trimethyl(2,3,4,5,6-pentamethyl-6H-cyclopentan-[b]thiophene-6-yl)silane in 100 mL of dichloromethane at -78 °C with vigorous stirring. The resulting mixture was stirred overnight at room temperature and then evaporated to dryness. Further, 150 mL of toluene was added to the residue, and the resulting mixture was filtered through a diatomaceous earth mat. The filtrate was evaporated to about 15 mL, and then 150 mL of hexane was added. The resulting mixture was cooled to -30 °C and then filtered through a glass frit (G3). The precipitate was washed with 2 × 30 mL of cold hexane and then dried under vacuum. This procedure yielded 2.93 g (54%) of a deep blue powder.

[0295] 1 H NMR (CD2Cl2, 400MHz): δ2.67(s,3H), 2.56(s,3H), 2.51(s,3H), 2.45(s,3H), 2.38(s,3H).

[0296] 1.2.10. Synthesis of trichloro(1,2,3-trimethylbenzo[b]cyclopentane[d]thiopheneyl)titanium

[0297]

[0298] A solution of 9.90 g (52 mmol) of titanium tetrachloride in 100 mL of dichloromethane was added dropwise to a solution of 14.8 g (52 mmol) of trimethyl-3H-benzo[b]cyclopentan-[d]thiophene-3-yl)silane in 300 mL of dichloromethane at -78 °C with vigorous stirring. The resulting mixture was stirred overnight at room temperature and then evaporated to dryness. Further, 350 mL of toluene was added to the residue, and the resulting mixture was filtered through a diatomaceous earth mat. The filtrate was evaporated to about 150 mL, and 350 mL of hexane was added. The resulting mixture was cooled to -30 °C and then filtered through a glass frit (G3). The precipitate was washed with 2 × 100 mL of cold hexane and then dried under vacuum. This procedure yielded 15.8 g (83%) of a dark purple powder.

[0299] 1H NMR (CD2Cl2, 400MHz): δ8.09-8.11(m,1H),7.84-7.86(m,1H),7.52-7.57(m,2H),2.82(s,3H),2.64(s,3H),2.52(s,3H).

[0300] 1.2.11. Synthesis of [3-bromo-2,4,5,6-tetramethylcyclopentane[b]thiophene](trichloro)titanium

[0301]

[0302] To a suspension of 2.35 g (58.7 mmol) of dry potassium hydride in 250 mL of THF, a solution of 15 g (58.7 mmol) of 3-bromo-2,4,5,6-tetramethyl-4H-cyclopentane[b]thiophene in 50 mL of THF was slowly added. The resulting mixture was stirred at 50 °C for 4 hours and then filtered through a diatomaceous earth mat. The filtrate was evaporated to dryness. The residue was ground with 25 mL of hexane, and the resulting mixture was filtered through a glass frit. The potassium salt thus obtained was washed with 2 × 10 mL of hexane and dried under vacuum. The resulting powder was dissolved in 400 mL of THF, and the resulting solution was cooled to -30 °C. While stirring vigorously, a solution of 15.0 g (58.7 mmol) of tris(isopropoxy)titanium chloride in 100 mL of THF was added. The resulting mixture was stirred overnight at room temperature, filtered through a diatomaceous earth mat, and then evaporated to dryness. The residue was dissolved in 700 ml of toluene, and 44.9 g (264 mmol) of silicon tetrachloride was added. The resulting mixture was stirred at 60 °C for 4 hours, and then evaporated to dryness. The residue was dissolved in 300 ml of toluene, and the resulting solution was filtered through a diatomaceous earth mat. The filtrate was evaporated to about 50 ml, and 250 ml of hexane was added. The resulting suspension was cooled to -30 °C, and the precipitate was collected by filtration through a glass frit. The precipitate was washed with 2 × 100 ml of cold hexane, and then dried under vacuum. This procedure yielded 18.8 g (78%) of a deep purple powder.

[0303] 1 H NMR (CDCl3, 400MHz): δ2.74(s,3H), 2.57(s,3H), 2.55(s,3H), 2.43(s,3H).

[0304] 1.2.12. Synthesis of (3-bromo-4,5,6-trimethylcyclopentane[b]thiopheneyl)(trichloro)titanium

[0305]

[0306] To a suspension of 165 mg (4.1 mmol) of dry potassium hydride in 5 mL of THF, a solution of 1.00 g (4.1 mmol) of 3-bromo-4,5,6-trimethyl-4H-cyclopentyl[b]thiophene in 10 mL of THF was slowly added. The resulting mixture was stirred at 50 °C for 4 hours and then filtered through a diatomaceous earth mat. The filtrate was evaporated to dryness. The residue was ground with 25 mL of hexane, and the resulting mixture was filtered through a glass frit (G3). The potassium salt thus obtained was washed with 2 × 10 mL of hexane and dried under vacuum. It was then dissolved in 15 mL of THF, and the resulting solution was cooled to -30 °C while adding a solution of 1.07 g (4.1 mmol) of tris(isopropoxy)titanium chloride in 10 mL of THF with vigorous stirring. The resulting mixture was stirred overnight at room temperature, filtered through a diatomaceous earth mat, and then evaporated to dryness. The residue was dissolved in 20 ml of toluene, and 3.13 g (18.5 mmol) of silicon tetrachloride was added. The resulting mixture was stirred at 60 °C for 4 hours, and then evaporated to dryness. The residue was dissolved in 30 ml of toluene, and the resulting solution was filtered through a diatomaceous earth mat. The filtrate was evaporated to about 5 ml, and 30 ml of hexane was added. The resulting suspension was cooled to -30 °C, and the precipitate was collected by filtration through a glass frit (G3). The precipitate was washed with 2 × 15 ml of cold hexane, and then dried under vacuum. This procedure yielded 920 mg (57%) of a purple powder.

[0307] 1 ¹H NMR (triisopropoxy complex, C6D6, 400 MHz): δ 6.60 (s, 1H), 4.56–4.65 (sept, J = 6.1 Hz, 3H), 2.43 (s, 3H), 2.09 (s, 3H), 1.98 (s, 3H), 1.13–1.16 (m, 18H).

[0308] 1 ¹H NMR (trichloride complex, CD₂Cl₂, 400 MHz): δ 7.63 (s, 1H), 2.75 (s, 3H), 2.61 (s, 3H), 2.45 (s, 3H).

[0309] 1.2.13.(η 5 Synthesis of 2,3,5,6-Tetramethylcyclopentane[b]thiopheneyl)titanium trichloride (IV)

[0310]

[0311] To a solution of 3.56 g (20.0 mmol) of 2,3,5,6-tetramethyl-4H-cyclopentadienyl[b]thiophene in 200 mL of THF, 8.00 mL of a 2.5 M (20.0 mmol) solution of n-butyllithium in hexane was added. The resulting solution was stirred at room temperature for 1 hour, cooled to -80 °C, and 5.20 g (20.0 mmol) of tris(isopropoxy)titanium chloride was added. The reaction mixture was stirred overnight at room temperature and then evaporated to dryness. The crude tris(isopropoxy)thiophene-fused cyclopentadienyl titanium was dissolved in 180 mL of anhydrous toluene, and 17.0 g (100 mmol) of SiCl4 was added. The resulting suspension was stirred overnight at 60 °C and then evaporated to dryness. 140 mL of dichloromethane was added to the residue, and the resulting suspension was filtered through a diatomaceous earth 503 pad. The filtrate was evaporated to dryness, and the crude product was recrystallized from 350 ml of methylcyclohexane. Yield: 5.65 g (85%) purple powder.

[0312] 1 H NMR (CDCl3, 400MHz): δ6.65(s,1H),2.54(s,3H),2.50(s,3H),2.48(s,3H),2.24(s,3H)

[0313] 1.2.14.(η 5 Synthesis of 2,3,5-trimethyl-6-phenylcyclopentane[b]thiopheneyl)titanium trichloride (IV)

[0314]

[0315] At -50°C, 7.29 mL of a 2.5 M (18.2 mmol) solution of n-butyllithium in hexane was added to a solution of 4.38 g (18.2 mmol) of 2,3,5-trimethyl-6-phenyl-4H-cyclopentadienyl[b]thiophene in 200 mL of THF. The resulting solution was stirred at room temperature for 1 hour, then cooled to -80°C, and 4.75 g (18.2 mmol) of tris(isopropoxy)titanium chloride was added. The reaction mixture was stirred overnight at room temperature and then evaporated to dryness. The crude tris(isopropoxy)thiophene-fused cyclopentadienyl titanium was dissolved in 180 mL of anhydrous toluene, and 15.5 g (91.1 mmol) of SiCl4 was added. The resulting suspension was stirred overnight at 60°C and then evaporated to dryness. 140 mL of dichloromethane was added to the residue, and the resulting suspension was filtered through a diatomaceous earth 503 pad. The filtrate was evaporated to dryness, and the crude product was recrystallized from 250 ml of methylcyclohexane. Yield: 6.74 g (94%) purple powder.

[0316] 1H NMR (CDCl3, 400MHz): δ7.74 (d, J = 7.2Hz, 2H), 7.51 (t, J = 7.6Hz, 2H), 7.37-7.47 (m, 1H), 6.77 (s, 1H), 2.79 (s, 3H), 2.50 (s, 3H), 2.30 (s, 3H).

[0317] 1.2.15.[η 5 Synthesis of 2,3,5-trimethyl-6-(4-fluorophenyl)-cyclopentane[b]thiophene]titanium trichloride (IV)

[0318]

[0319] To a solution of 4.83 g (18.7 mmol) of 2,3,5-trimethyl-6-(4-fluorophenyl)-4H-cyclopentyl[b]thiophene in 200 mL of THF, 7.48 mL of a 2.5 M (18.7 mmol) solution of n-butyllithium in hexane was added. The resulting solution was stirred at room temperature for 1 hour, then cooled to -80 °C, and 4.87 g (18.7 mmol) of tris(isopropoxy)titanium chloride was added. The reaction mixture was stirred overnight at room temperature and then evaporated to dryness. The crude tris(isopropoxy)thiophene-fused cyclopentadienyl titanium was dissolved in 180 mL of anhydrous toluene, and 15.9 g (93.5 mmol) of SiCl4 was added. The resulting suspension was stirred overnight at 60 °C and then evaporated to dryness. 200 mL of dichloromethane was added to the residue, and the resulting suspension was filtered through a diatomaceous earth 503 pad. The filtrate was evaporated to dryness, and the crude product was recrystallized from 250 ml of methylcyclohexane. Yield: 6.37 g (83%) purple powder.

[0320] 1 H NMR (CDCl3, 400MHz): δ7.72 (dd, J=8.1, 5.7Hz, 2H), 7.20 (t, J=8.5Hz, 2H), 6.77 (s, 1H), 2.76 (s, 3H), 2.50 (s, 3H), 2.30 (s, 3H).

[0321] 1.2.16.(η 5 Synthesis of 2,3,5-trimethyl-6-isopropylcyclopentane[b]thiopheneyl)titanium trichloride (IV)

[0322]

[0323] To a solution of 1.03 g (5.00 mmol) of 2,3,5-trimethyl-6-isopropyl-4H-cyclopentane[b]thiophene in 50 mL of THF, 2.00 mL of a 2.5 M (5.00 mmol) n-butyllithium solution in hexane was added. The resulting solution was stirred at room temperature for 1 hour, then cooled to -80 °C, and 1.30 g (5.00 mmol) of tris(isopropoxy)titanium chloride was added. The reaction mixture was stirred overnight at room temperature and then evaporated to dryness. The crude tris(isopropoxy)thiophene-fused cyclopentadienyl titanium was dissolved in 50 mL of anhydrous toluene, and 4.24 g (25.0 mmol) of SiCl4 was added. The resulting suspension was stirred overnight at 60 °C and then evaporated to dryness. 50 mL of dichloromethane was added to the residue, and the resulting suspension was filtered through a diatomaceous earth 503 pad. The filtrate was evaporated to dryness, and the crude product was recrystallized from 80 ml of methylcyclohexane. Yield: 1.00 g (56%) purple powder.

[0324] 1 H NMR (CDCl3, 400MHz): δ6.70 (s, 1H), 3.46 (sept, J = 6.8 Hz, 1H), 2.52 (s, 3H), 2.47 (s, 3H), 2.23 (s, 3H), 1.53 (d, J = 6.9 Hz, 3H), 1.18 (d, J = 7.0 Hz, 3H).

[0325] 1.3. Synthesis of titanium dichloride amidine complexes with noncyclic amidine groups

[0326] A general procedure for tethering non-cyclic amidine ligands:

[0327] At room temperature, 1 equivalent of amidine and 5 equivalents of trimethylamine were added to a solution of the metal precursor in 200 mL of toluene. The resulting mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was dissolved in 200 mL of toluene, and the resulting mixture was filtered through a diatomaceous earth mat. The filtrate was concentrated to 20 mL, and 150 mL of pentane was added. The resulting suspension, cooled to -30 °C, was filtered, and the precipitate was washed with 2 x 50 mL of cold pentane, followed by vacuum drying. The resulting powder was recrystallized from a pentane:hexane mixture (1:5) at -30 °C.

[0328] 1.3.1. Comparative Example 1: Synthesis of (1,2,3-trimethyl-benzo[b]cyclopentane[d]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride (CE 1) known from KR20170046462

[0329]

[0330] As described in the general procedure at the beginning of this section, the complex was obtained starting from trichloro(1,2,3-trimethylbenzo[b]cyclopentane[d]thiophene)titanium (4.02 g, 10.9 mmol), 1-(2,6-difluorophenyl)-1-piperidin-1-ylmethylimine (2.44 g, 10.9 mmol), triethylamine (5.52 g, 54.4 mmol), and 70 ml of toluene. The yield was 3.82 g (63%) of a dark orange powder.

[0331] 1 H NMR (CD2Cl2, 400MHz): δ7.87-7.89(m,1H),7.69-7.71(m,1H),7.30-7.41(m,3H),6.96-7.00(m,2H ),3.29-3.42(m,2H),3.09-3.19(m,2H),2.48(s,3H),2.23(s,3H),2.21(s,3H),1.49-1.63(m,6H).

[0332] 19 F NMR (CD2Cl2, 376MHz): δ-111.15(m,1F),-111.22(m,1F).

[0333] 1.3.2. Synthesis of (2,3,4,5,6-pentamethyl-cyclopentane[b]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride (compound 1)

[0334]

[0335] As described in the general procedure at the beginning of this section, the compound was obtained starting from trichloro(2,3,4,5,6-pentamethylcyclopentane[b]thiophene)titanium (3.98 g, 11.5 mmol), 1-(2,6-difluorophenyl)-1-piperidin-1-ylmethylimine (2.58 g, 11.5 mmol), triethylamine (5.82 g, 57.6 mmol), and 100 ml of toluene. This procedure yielded 5.40 g (88%) of a yellow powder.

[0336] 1 H NMR (CD2Cl2, 400MHz): δ7.34-7.41(m,1H),6.97-7.01(m,2H),3.65-3.67(m,2H),3 .19-3.21(m,2H),2.33(s,3H),2.32(s,3H),2.22(s,3H),2.13(s,3H),2.13(s,3H).

[0337] 19F NMR (CD2Cl2, 376MHz): δ-111.39 (m, 1F), -111.48 (m, 1F).

[0338] 1.3.3. Synthesis of (3-bromo-4,5,6-trimethylcyclopentane[b]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride (compound 3)

[0339]

[0340] As described in the general procedure at the beginning of this section, the complex was obtained starting with (3-bromo-4,5,6-trimethyl-cyclopentane[b]thiopheneyl)(trichloro)titanium (5.96 g, 15.0 mmol), 1-(2,6-difluorophenyl)-1-piperidin-1-ylmethylimine (3.36 g, 15.0 mmol), triethylamine (7.59 g, 75.0 mmol), and 250 ml of toluene. This procedure yielded 7.80 g (89%) of an orange powder.

[0341] 1 H NMR (CD2Cl2, 400MHz): δ7.30-7.37(m,1H),7.11(s,1H),6.93-6.97(m,2H),3.66-3.77(m,2H),3 .18-3.21(m,2H),2.43(s,3H),2.22(s,3H),2.11(s,3H),1.63-1.76(m,4H),1.54-1.59(m,2H),

[0342] 19 F NMR (CD2Cl2, 376MHz): δ-110.03(m,1F),-110.12(m,1F).

[0343] 1.3.4. Synthesis of (3-bromo-2,4,5,6-tetramethylcyclopentane[b]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride (compound 5)

[0344]

[0345] As described in the general procedure at the beginning of this section, the compound was obtained starting with (3-bromo-2,4,5,6-tetramethyl-cyclopentane[b]thiopheneyl)(trichloro)titanium (5.55 g, 13.5 mmol), 1-(2,6-difluorophenyl)-1-piperidin-1-ylmethylimine (3.02 g, 13.5 mmol), triethylamine (6.82 g, 67.4 mmol), and 250 ml of toluene. This procedure yielded 7.26 g (90%) of a red powder.

[0346] 1 H NMR (CDCl3, 400MHz): δ7.29-7.37(m,1H),6.92-6.98(m,2H),3.65-3.76(m,2H),3.18-3.20(m, 2H),2.43(s,3H),2.38(s,3H),2.19(s,3H),2.07(s,3H),1.63-1.75(m,4H),1.54-1.59(m,2H).

[0347] 19 F NMR (CDCl3, 376MHz): δ-110.24 (m).

[0348] 1.3.5. Synthesis of dichloro{4,5,6-trimethylcyclopentane[b]thiophene}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titaniumamine (compound 11)

[0349]

[0350] As described in the general procedure at the beginning of this section, the compound was obtained starting from trichloro(4,5,6-trimethylcyclopentane[b]thienyl)titanium (5.00 g, 15.8 mmol), (2,6-difluorophenyl)(piperidin-1-yl)methylimine (3.54 g, 15.8 mmol), triethylamine (7.97 g, 78.7 mmol), and 200 ml of toluene. This procedure yielded 4.70 g (59%) of a yellow powder.

[0351] 1 H NMR (CD2Cl2, 400MHz): δ7.39 (m, 1H), 7.28 (d, 1H, J = 4.9Hz), 6.92-7.02 (m, 3H), 3.63 (b r.s,2H),3.20(br.s,2H),2.23(s,6H),2.18(s,3H),1.68(br.s,4H),1.57(br.s,2H).

[0352] 1.3.6. Synthesis of dichloro{3-(2-isopropylphenyl)-4,5,6-trimethylcyclopentane[b]thiophene}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titaniumamine (compound 13)

[0353]

[0354] As described in the general procedure at the beginning of this section, the compound was obtained starting with trichloro(3-(2-isopropylphenyl)-2,4,5,6-trimethylcyclopentane[b]thiophene)titanium (1.65 g, 3.7 mmol), (2,6-difluorophenyl)(piperidin-1-yl)methylimine (820 mg, 3.7 mmol), triethylamine (1.86 g, 18.4 mmol), and 100 ml of toluene. This procedure yielded 1.56 g (67%) of a yellow powder.

[0355] 1H NMR (CD2Cl2, 400MHz): δ7.28-7.41(m,3H),7.11-7.15(m,1H),6.98(m,3H),3.67(br.s,2H),3.18(m,2H),2.73(sept,1H,J=6.9Hz) ,2.29(s,3H),2.18(s,3H),1.94(s,3H),1.83(s,3H),1.66(br.s,4H),1.55(br.s,2H),1.10(d,3H,J=6.9Hz),1.04(d,3H,J=6.9Hz)

[0356] 1.3.7. Synthesis of dichloro{3-(4-dimethylaminophenyl)-4,5,6-trimethylcyclopentane[b]thiophene}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titaniumamine (compound 15)

[0357]

[0358] As described in the general procedure at the beginning of this section, the compound was obtained starting with trichloro(3-(4-dimethylaminophenyl)-4,5,6-trimethylcyclopentane[b]thiophene)titanium (2.45 g, 5.61 mmol), (2,6-difluorophenyl)(piperidin-1-yl)methylimine (1.26 g, 5.61 mmol), triethylamine (3.62 g, 28.1 mmol), and 150 ml of toluene. This procedure yielded 2.00 g (57%) of a yellow powder.

[0359] 1 H NMR (CD2Cl2, 400MHz): δ7.35 (m, 1H), 7.29 (d, 2H, J = 8.9Hz), 7.03 (s, 1H), 6.91-7.00 (m, 2H), 6.67 (d, 2H, J = 8.9Hz), 3.68(br.s,2H),3.18(m,2H),2.97(s,6H),2.29(s,3H),2.18(s,3H),2.10(s,3H),1.67(br.s,4H),1.55(br.s,2H),

[0360] 1.3.8. Synthesis of {3-(3,5-di-tert-butylphenyl)-4,5,6-trimethylcyclopentane[b]thiophene}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride (compound 7)

[0361]

[0362] To a solution of 7.1 mL of 3,5-di-tert-butylphenyl magnesium bromide (4.16 mmol, 0.588 M) in THF, add 570 mg (4.16 mmol) of ZnCl2 in 10 mL of THF. Stir the resulting mixture at room temperature for 1 hour, then add 9 mg (0.015 mmol) of Pd(PtBu3)2 in 2 mL of diethyl ether. Heat the resulting mixture to reflux, then add 2.33 g (4.00 mmol) of (3-bromo-4,5,6-trimethyl-cyclopentane-[b]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride in 40 mL of THF. Stir the resulting mixture overnight at 40 °C. Then quench it with 10.0 mL of trimethylchlorosilane and evaporate to dryness. Add 100 mL of toluene to the residue. The mixture was refluxed for 30 minutes and then filtered through a diatomaceous earth pad. The resulting filtrate was evaporated to approximately 30 ml. The crystals precipitated from the solution at -30°C were collected, washed with 50 ml of cold hexane, and dried under vacuum. This procedure yielded 2.69 g (97%) of a dark red crystalline substance.

[0363] 1 H NMR (CDCl3, 400MHz): δ7.34-7.37(m,3H),7.23-7.30(m,1H),7.13(s,1H),6.87-6.91(m,2H),3.57-3. 70(m,2H),3.13-3.16(m,2H),2.28(s,3H),2.17(s,3H),2.07(s,3H),1.50-1.67(m,6H),1.31(s,18H).

[0364] 19 F NMR(C6D6,376MHz): δ-110.31(m,1F),-110.66(m,1F).

[0365] 1.3.9. Synthesis of {3-(3,5-di-tert-butylphenyl)-2,4,5,6-tetramethylcyclopentane[b]thiopheneyl}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride (compound 9)

[0366]

[0367] As described for {3-(3,5-di-tert-butylphenyl)-4,5,6-trimethyl-cyclopentane[b]thienyl}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride, the complex was obtained starting from (3-bromo-2,4,5,6-tetramethyl-cyclopentane[b]thienyl)[(2,6-difluorophenyl)-(piperidin-1-yl)methylene]titanium dichloride (1.80 g, 3.00 mmol), 3,5-di-tert-butylphenyl magnesium bromide (5.31 ml, 3.12 mmol, 0.588 M THF solution), ZnCl2 (425 mg, 3.12 mmol), Pd(PtBu3)2 (6 mg, 0.011 mmol), 15.0 ml of trimethylchlorosilane and 40 ml of THF. The crude product was recrystallized from toluene at -30°C to give 2.08 g (98%) of red crystalline solid.

[0368] 1 H NMR(CDCl3,400MHz): δ7.28-7.34(m,2H),7.08-7.55(br.s,2H),6.90-6.95(m,2H),3.60-3.73(m,2H),3 .15-3.18(m,2H),2.35(s,3H),2.26(s,3H),2.02(s,3H),1.95(s,3H),1.53-1.69(m,6H),1.31(s,18H).

[0369] 19 F NMR(C6D6,376MHz): δ-110.31(m,1F),-110.66(m,1F).

[0370] 1.3.10. Synthesis of dichloro{3-(4-dimethylaminophenyl)-2,4,5,6-tetramethyl-cyclopentane[b]thiophene}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titaniumamine (compound 18)

[0371]

[0372] As described for {3-(3,5-di-tert-butylphenyl)-4,5,6-trimethyl-cyclopentane[b]thienyl}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride, the complex was obtained starting from (3-bromo-2,4,5,6-tetramethyl-cyclopentane[b]thienyl)[(2,6-difluorophenyl)-(piperidin-1-yl)methylene]titanium dichloride (1.20 g, 2.00 mmol), 3,5-di-tert-butylphenyl magnesium bromide (5.35 ml, 4 mmol), ZnCl2 (600 mg, 4.4 mmol), Pd(PtBu3)2 (51 mg, 0.10 mmol), 10.0 ml of trimethylchlorosilane, and 40 ml of THF. The crude product was recrystallized from toluene at -30 °C to give 870 mg (68%) of a red crystalline solid.

[0373] 1 H NMR (CD2Cl2, 400MHz): δ7.34-7.47(m,2H),7.16(d,2H,J=8.4Hz),6.99(m,1H),6.70(d,2H,J=8.4Hz),3.69(br.s,2H ),3.19(br.s,2H),2.98(s,6H),2.32(s,3H),2.26(s,3H),2.03(s,3H),1.98(s,3H),1.67(br.s,4H),1.56(br.s,2H)

[0374] 1.3.11. Synthesis of {3-(4-methylphenyl)-2,4,5,6-tetramethylcyclopentane[b]thiophene}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride (compound 17)

[0375]

[0376] Add 51.0 mg (0.10 mmol) of Pd (P) to a solution of 0.53 M p-tolyl magnesium bromide in THF (34.2 ml, 17.1 mmol). tA solution of Bu3)2 in 5 ml of diethyl ether was added. The resulting mixture was stirred at room temperature for 15 minutes, then heated to reflux, and 2.05 g (3.42 mmol) of a solution of (dimethyl)(3-bromo-4,5,6-trimethylcyclopentane[b]-thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titaniumamine in 40 ml of diethyl ether was added under reflux. The resulting mixture was stirred overnight at 40 °C and then evaporated to dryness. 25 ml of toluene was added to the residue. The resulting mixture was refluxed for 30 minutes and then evaporated to dryness. The residue was ground in 100 ml of hexane, and the resulting suspension was filtered through a diatomaceous earth 503 pad. The filtrate was evaporated to about 10 ml. The crystals precipitated from the solution at -30 °C were collected, washed with 2 × 15 ml of cold hexane, and dried under vacuum. This procedure yielded 1.75 g (90%) of yellow crystals.

[0377] 1 H NMR (C6D6, 400MHz): δ7.31 (d, 2H, J = 8.1Hz), 7.02 (d, 2H, J = 8.1Hz), 6.46-6.58 (m, 3H), 3.70 (br.s, 2H), 2.90 (br.s, 2H), 2. 26(s,3H),2.20(s,3H),2.16(s,3H),1.97(s,3H),1.75(s,3H),1.40(br.s,2H),1.16(br.s,4H),0.65(s,3H),0.60(s,3H).

[0378] 1.3.12. Dichloro(η) 5 Synthesis of -2,2,5,6,7-pentamethyl-1,2,3-trihydrodicyclopentane-[b,d]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium(IV)amine (compound 27)

[0379]

[0380] As described in the general procedure at the beginning of this section, the complex is obtained.

[0381] Yield: 52%

[0382] 1H NMR (CD2Cl2, 400MHz): δ7.37(m,1H),6.99(m,2H),3.67(m,2H),3.20(m,2H),2.55-2.68(m,4H),2 .26(s,3H),2.13(s,3H),2.11(s,3H),1.68(br.s,4H),1.56(br.s,2H),1.24(s,3H),1.21(s,3H).

[0383] 1.3.13. Dichloro(η) 5 Synthesis of -6,7,8-trimethyl-1,2,3,4-tetrahydrocyclohexano[b]cyclopentan-[d]thienyl)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titaniumamine (Cpd 24)

[0384]

[0385] As described in the general procedure at the beginning of this section, the complex is obtained.

[0386] Yield: 62%

[0387] 1 H NMR(CD2Cl2,400MHz): δ7.40(m,1H),6.89(m,2H),3.65(br.s,2H),3.14(br.s,2H),2.80-2.90(m,1H),2.5 4-2.68(m,2H),2.45-2.48(m,1H),2.29(s,3H),2.14(s,3H),1.78(s,3H),1.65(br.s,4H),1.45(br.s,2H).

[0388] 1.3.14. Dichloro(η) 5 Synthesis of 2-phenyl-3,4,5,6-tetramethylcyclopentane[b]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium(IV)amine (compound 28)

[0389]

[0390] As described in the general procedure at the beginning of this section, the complex is obtained.

[0391] Yield: 75%

[0392] 1 H NMR(CD2Cl2,400MHz): δ7.35-7.44(m,6H),6.98(m,2H),3.66(br.s,2H),3.20(br.s,2H ),2.40(s,3H),2.36(s,3H),2.21(s,3H),2.14(s,3H),1.64(br.s,4H),1.55(br.s,2H).

[0393] 1.3.15. Dichloro[η] 5 Synthesis of -2-(3,5-di-tert-butylphenyl)-3,4,5,6-tetramethylcyclopentan-[b]thiophene][(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium(IV)amine (compound 29)

[0394]

[0395] As described in the general procedure at the beginning of this section, the complex is obtained.

[0396] Yield: 64%

[0397] 1 H NMR (CD2Cl2, 400MHz): δ7.43(t,1H,J4=1.7Hz),7.37(m,1H),7.29(s,1H),7.28(s,1H),6.99(m,2H),3.58-3.71(m,2 H),3.20(m,2H),2.41(s,3H),2.40(s,3H),2.20(s,3H),2.15(s,3H),1.65(br.s,4H),1.56(br.s,2H),1.36(s,18H).

[0398] 1.3.16. Dichloro[η] 5 Synthesis of -2-(2-isopropylphenyl)-3,4,5,6-tetramethylcyclopentan-[b]thiophene][(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium(IV)amine (compound 30)

[0399]

[0400] As described in the general procedure at the beginning of this section, the complex is obtained.

[0401] Yield: 82%

[0402] 1 H NMR (CD2Cl2, 400MHz): δ7.34-7.43(m,3H),7.14-7.26(m,2H),7.00(m,2H),3.78(br.s,2H),3.12-3.33(m,3H),3.29(b r.s,3H),2.24(br.s,3H),2.15(br.s,3H),2.08(br.s,3H),1.68-1.73(m,4H),1.58(br.s,2H),1.14(d,6H,J=6.6Hz).

[0403] 1.3.17. Dichloro(η) 5 Synthesis of 2-cyclohexyl-3,4,5,6-tetramethylcyclopentane[b]thiophene)[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium(IV)amine (compound 31)

[0404]

[0405] As described in the general procedure at the beginning of this section, the complex is obtained.

[0406] Yield: 77%

[0407] 1 H NMR (CD2Cl2, 400MHz): δ7.38 (m, 1H), 6.96-7.03 (m, 2H), 3.71 (br.s, 2H), 3.20 (br.s, 2H), 2.85 (ddd, 1H, J1=11.4Hz, J2=8.0Hz, J3=3.5Hz ),2.35(s,3H),2.24(s,3H),2.20(s,3H),2.09(s,3H),1.78-1.89(m,4H),1.67-1.73(m,5H),1.56(br.s,2H),1.39(m,3H),1.30(m,2H).

[0408] 1.4. Synthesis of titanium dichloride amidine complexes with cyclic amidine ligands

[0409] A general procedure for tethering cyclic amidine ligands:

[0410] At room temperature, an amidine ligand (1 equivalent) and trimethylamine (5 equivalents) were added to a solution of the metal precursor in 70 mL of toluene. The mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was dissolved in 150 mL of toluene, and the resulting mixture was filtered through a diatomaceous earth mat. The filtrate was then evaporated to 15 mL, and 100 mL of hexane was added to allow crystallization at -30 °C. The crystals were separated by filtration, washed with 2 x 50 mL hexane, and then dried under vacuum.

[0411] 1.4.1. Synthesis of (2,3,4,5,6-pentamethylcyclopentane[b]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium dichloride (compound 2)

[0412]

[0413] Using the procedure described at the beginning of this section, the complex was synthesized from (2,3,4,5,6-pentamethylcyclopentane[b]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindoline-1-imine]titanium dichloride and 2-(2,6-dimethylphenyl)-isoindoline-1-imine as starting materials. The reaction yielded a 65% dark red powder.

[0414] 1H NMR (CD2Cl2, 400MHz): δ7.65-7.67(m,1H),7.58-7.61(m,1H),7.47-7.54(m,2H),7.20-7.24(m,1H),7.15-7.17(m, 2H),4.69-4.85(m,2H),2.37(s,3H),2.29(s,3H),2.28(s,3H),2.24(s,3H),2.20(s,3H),2.04(s,3H),1.87(s,3H).

[0415] 1.4.2. Synthesis of (3-bromo-4,5,6-trimethylcyclopentane[b]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium dichloride (compound 4)

[0416]

[0417] As described in the general procedure at the beginning of this section, the complex was obtained starting with (3-bromo-4,5,6-trimethylcyclopentane[b]thiophene)(trichloro)titanium (1.98 g, 4.98 mmol), 2-(2,6-dimethylphenyl)isoindoline-1-imine (1.17 g, 4.98 mmol), triethylamine (2.52 g, 24.9 mmol), and 100 ml of toluene. This procedure yielded 1.84 g (62%) of a red powder.

[0418] 1 H NMR (CD2Cl2, 400MHz): δ7.84-7.86(m,1H),7.57-7.61(m,1H),7.48-7.52(m,2H),7.21-7.23(m,1H),7.15 -7.17(m,2H),7.09(s,1H),4.75(s,2H),2.37(s,3H),2.35(s,3H),2.33(s,3H),2.05(s,3H),2.00(s,3H).

[0419] 1.4.3. Synthesis of (3-bromo-2,4,5,6-tetramethylcyclopentane[b]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium dichloride (compound 6)

[0420]

[0421] As described in the general procedure at the beginning of this section, the complex was obtained starting with (3-bromo-2,4,5,6-tetramethylcyclopentane[b]thiopheneyl)(trichloro)-titanium (1.79 g, 4.36 mmol), 2-(2,6-dimethylphenyl)isoindoline-1-imine (1.05 g, 4.36 mmol), triethylamine (2.21 g, 21.8 mmol), and 100 ml of toluene. This procedure yielded 1.65 g (62%) of a dark red powder.

[0422] 1 H NMR(CDCl3,400MHz): δ7.73-7.75(m,1H),7.55-7.59(m,1H),7.46-7.50(m,2H),7.14-7.21(m,3 H),4.74(s,2H),2.35(s,3H),2.35(s,3H),2.33(s,3H),2.26(s,3H),1.98(s,3H),1.97(s,3H).

[0423] 1.4.4. Synthesis of dichloro[4,5,6-trimethylcyclopentane[b]thiophene)][2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titaniumamine (compound 12)

[0424]

[0425] As described in the general procedure at the beginning of this section, the complex was obtained starting with trichloro(4,5,6-trimethylcyclopentane[b]thiophene)titanium (5.00 g, 15.8 mmol), 2-(2,6-dimethylphenyl)isoindoline-1-imine (3.72 g, 15.8 mmol), triethylamine (7.97 g, 78.7 mmol), and 150 ml of toluene. This procedure yielded 4.70 g (58%) of a dark red powder.

[0426] 1 H NMR (CD2Cl2, 400MHz): δ7.76 (d, 1H, J = 7.5Hz), 7.61 (m, 1H), 7.49-7.54 (m, 2H), 7.17-7.25 (m, 4H), 6 .89(d,1H,J=4.5Hz),4.77(m,2H),2.34(s,3H),2.31(s,3H),2.16(s,3H),2.09(s,3H),2.07(s,3H).

[0427] 1.4.5. Synthesis of dichloro[3-(2-isopropylphenyl)-2,4,5,6-tetramethylcyclopentane[b]thiophene)][2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titaniumamine (compound 14)

[0428]

[0429] As described in the general procedure at the beginning of this section, the complex was obtained starting with dichloro(2,3,4,5,6-pentamethylcyclopentane[b]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindoline-1-imine]titanium (2.00 g, 4.5 mmol), 2-(2,6-dimethylphenyl)isoindoline-1-imine (1.1 g, 4.5 mmol), triethylamine (2.25 g, 22.3 mmol), and 150 ml of toluene. This procedure yielded 1.04 g (36%) of a dark red powder.

[0430] 1 H NMR (CD2Cl2, 400MHz): δ7.81(d,1H,J=7.5Hz),7.59-7.62(m,1H),7.42-7.54(m,2H),7.35-7.42(m,3H),7.12-7.29(m,4H),4.75(m,2H),2.70( sept,1H,J=6.9Hz),2.34(s,3H),2.27(s,3H),2.16(s,3H),2.13(s,3H),1.80(s,3H),1.75(s,3H),1.09(d,3H,J=6.9Hz),1.02(d,3H,J=6.9Hz)

[0431] 1.4.6. Synthesis of dichloro[(3-(4-dimethylaminophenyl)-4,5,6-trimethylcyclopentane[b]thiophene)][2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titaniumamine (compound 16)

[0432]

[0433] As described in the general procedure at the beginning of this section, the complex was obtained starting with trichloro(3-(4-dimethylaminophenyl)-4,5,6-trimethylcyclopentane[b]thiophene)titanium (3.12 g, 7.14 mmol), 2-(2,6-dimethylphenyl)isoindoline-1-imine (1.69 g, 7.14 mmol), triethylamine (3.62 g, 35.7 mmol), and 150 ml of toluene. This procedure yielded 2.06 g (45%) of a dark red powder.

[0434] 1 H NMR (CD2Cl2, 400MHz): δ7.76(d,1H,J=7.7Hz),7.59(m,1H),7.41-7.52(m,3H),7.32(d,2H,J=8.8Hz),7.23(m,2H),7.00( s,1H),6.71(d,2H,J=8.8Hz),4.74(m,2H),2.99(s,6H),2.32(s,3H),2.22(s,3H),2.18(s,3H),2.10(s,3H),1.95(s,3H).

[0435] 1.4.7. Synthesis of {3-(3,5-di-tert-butylphenyl)-4,5,6-trimethylcyclopentane[b]thiophene}[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium dichloride (compound 8)

[0436]

[0437] As described for {3-(3,5-di-tert-butylphenyl)-4,5,6-trimethyl-cyclopentane[b]thiopheneyl}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride, the complex was obtained starting from (3-bromo-4,5,6-trimethylcyclopentane[b]thiopheneyl)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindol-1-ylidene]titanium dichloride (1.40 g, 2.36 mmol), 3,5-di-tert-butylphenyl magnesium bromide (4.17 ml, 2.45 mmol, 0.588 M THF solution), ZnCl2 (334 mg, 2.45 mmol), Pd(PtBu3)2 (5 mg, 0.009 mmol), 8.0 ml of trimethylchlorosilane and 30 ml of THF. The crude product was recrystallized from toluene at -30°C to obtain 1.53 g (92%) of dark brown crystalline substance.

[0438] 1 H NMR (CDCl3, 400MHz): δ7.75-7.77(m,1H),7.53-7.57(m,1H),7.41-7.47(m,2H),7.36-7.39(m,3H),7.08-7.1 9(m,4H),4.63-4.75(m,2H),2.33(s,3H),2.17(s,3H),2.11(s,3H),2.08(s,3H),1.96(s,3H),1.31(s,18H).

[0439] 1.4.8. Synthesis of dichloro[3-(3,5-di-tert-butylphenyl)-2,4,5,6-tetramethylcyclopentan-[b]thiophene)][2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titaniumamine (compound 10)

[0440]

[0441] As described for {3-(3,5-di-tert-butylphenyl)-4,5,6-trimethyl-cyclopentane[b]thienyl}[(2,6-difluorophenyl)(piperidin-1-yl)methylene]titanium dichloride, the complex was obtained starting from (3-bromo-2,4,5,6-tetramethylcyclopentane[b]thienyl)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindol-1-ylidene]titanium dichloride (3.85 mmol), 3,5-di-tert-butylphenyl magnesium bromide (3.85 mmol, 0.588 M THF solution), ZnCl2 (3.85 mmol), Pd(PtBu3)2 (5 mg, 0.009 mmol), 8.0 ml of trimethylchlorosilane and 30 ml of THF. The crude product was recrystallized from toluene at -30°C to give 1.45 g (52%) of dark orange crystalline substance.

[0442] 1 H NMR (CD2Cl2, 400MHz): δ7.72 (d, 1H, J = 7.5Hz), 7.59 (m, 1H), 7.52 (d, 1H, J = 7.5Hz), 7.47 (t, 1H, J = 7.5Hz), 7.41 (t, 1H, J4 = 1.8Hz), 7 .11-7.26(m,5H),4.67-4.82(m,2H),2.36(s,3H),2.25(s,3H),2.16(s,3H),2.06(s,3H),1.94(s,3H),1.87(s,3H),1.33(s,18H).

[0443] 1.4.9. Dichloro(η) 5 Synthesis of -2,2,5,6,7-pentamethyl-1,2,3-trihydrodicyclopentane[b,d]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium(IV)amine (compound 32)

[0444]

[0445] Yield: 38%

[0446] 1H NMR (CD2Cl2, 400MHz): δ7.46-7.60(m,4H),7.28(m,2H),7.13(m,1H),4.70(s,2H),2.55-2 .68(m,4H),2.26(s,6H),2.15(s,3H),2.13(s,3H),2.11(s,3H),1.20(s,3H),1.19(s,3H).

[0447] 1.4.10. Dichloro(η) 5 Synthesis of -6,7,8-trimethyl-1,2,3,4-tetrahydrocyclohexano[b]cyclopentan-[d]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium(IV)amine (compound 25)

[0448]

[0449] As described in the general procedure at the beginning of this section, the complex is obtained.

[0450] Yield: 67%

[0451] 1 H NMR (CD2Cl2, 400MHz): δ7.67(m,1H),7.59(m,1H),7.49-7.54(m,2H),7.15-7.24(m,3H),4.68-4.86(m,2H),2.83-2.88(m,1 H),2.59-2.69(m,2H),2.47-2.48(m,1H),2.38(s,3H),2.29(s,3H),2.26(s,3H),2.04(s,3H),1.87(s,3H),1.79(br.s,4H).

[0452] 1.4.11. Dichloro(η) 5 Synthesis of 2-phenyl-3,4,5,6-tetramethylcyclopentane[b]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium(IV)amine (compound 33)

[0453]

[0454] As described in the general procedure at the beginning of this section, the complex is obtained.

[0455] Yield: 45%

[0456] 1H NMR (CD2Cl2, 400MHz): δ7.73 (d, 1H, J = 7.6Hz), 7.51-7.58 (m, 2H), 7.29-7.42 (m, 6H), 7.15-7.22 (m, 3 H),4.70-4.85(m,2H),2.37(s,3H),2.37(s,3H),2.36(s,3H),2.31(s,3H),2.05(s,3H),1.98(s,3H).

[0457] 1.4.12. Dichloro[η] 5 Synthesis of 2-(3,5-di-tert-butylphenyl)-3,4,5,6-tetramethylcyclopentan-[b]thiophene][2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium(IV)amine (compound 34)

[0458]

[0459] As described in the general procedure at the beginning of this section, the complex is obtained.

[0460] Yield: 52%

[0461] 1 H NMR (CD2Cl2, 400MHz): δ7.76 (d, 1H, J = 7.9Hz), 7.50-7.56 (m, 2H), 7.39-7.45 (m, 2H), 7.14-7.24 (m, 5H), 4.7 0-4.84(m,2H),2.39(s,3H),2.37(s,3H),2.36(s,3H),2.30(s,3H),2.06(s,3H),1.96(s,3H),1.31(s,18H).

[0462] 1.4.13. Dichloro(η) 5 Synthesis of 2-cyclohexyl-3,4,5,6-tetramethylcyclopentane[b]thiophene)[2-(2,6-dimethylphenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titanium(IV)amine (compound 26)

[0463]

[0464] As described in the general procedure at the beginning of this section, the complex is obtained.

[0465] Yield: 60%

[0466] 1H NMR (CD2Cl2, 400MHz): δ7.75(d,1H,J=7.7Hz),7.59(m,1H),7.51(m,2H),7.15-7.24(m,3H),4.69-4.83(m,2H),2.77(m,1H),2.36(s,3H),2 .30(s,3H),2.29(s,3H),2.23(s,3H),2.00(s,3H),1.94(s,3H),1.78-1.86(m,2H),1.69(br.s,2H),1.54-1.55(m,1H),1.18-1.39(m,5H).

[0467] 1.5. Synthesis of titanium dichloride amidine complex with fluorinated cyclic amidine ligands.

[0468] A general procedure for tethering cyclic amidine ligands:

[0469] At room temperature, an amidine ligand (1 equivalent) and trimethylamine (5 equivalents) were added to a solution of the metal precursor in 70 mL of toluene. The mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was dissolved in 150 mL of toluene, and the resulting mixture was filtered through a diatomaceous earth mat. The filtrate was then evaporated to 15 mL, and 100 mL of hexane was added to allow crystallization at -30 °C. The crystals were separated by filtration, washed with 2 x 50 mL hexane, and then dried under vacuum.

[0470] 1.5.1. Dichloro(η) 5 Synthesis of 2,3,5,6-Tetramethylcyclopentane[b]thiopheneyl)[2-(2,6-difluorophenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titaniumamine (compound 19)

[0471]

[0472] Synthesized using the method described at the beginning of this section. Yield: 1.96 g (86%).

[0473] 1 H NMR (CDCl3, 400MHz): δ7.64 (d, J=7.7Hz, 1H), 7.53-7.60 (m, 1H), 7.42-7.50 (m, 2H), 7.35 (tt, J=8.5, 6.1Hz, 1H), 7.05 (t, J=8 .4Hz,2H),6.15(s,1H),4.93(d,J=17.4Hz,1H),4.81(d,J=17.3Hz,1H),2.17(s,3H),2.07(s,3H),2.04(s,3H),1.98(s,3H).

[0474] 1.5.2. Dichloro(η) 5 Synthesis of 2,3,5-trimethyl-6-phenylcyclopentane[b]thiophene)[2-(2,6-difluorophenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titaniumamine (compound 20)

[0475]

[0476] Synthesized using the method described at the beginning of this section. Yield: 2.10 g (83%).

[0477] 1 H NMR (CDCl3, 400MHz): δ7.51 (d, J = 7.4Hz, 3H), 7.40 (d, J = 8.2Hz, 2H), 7.31-7.37 (m, 1H), 7.17-7.31 (m, 4H), 6.81-6.97(m,2H),6.31(s,1H),4.85(d,J=17.4Hz,1H),4.72(d,J=17.5Hz,1H),2.47(s,3H),2.12(m,6H). 1.5.3.Dichloro[eta 5 Synthesis of -2,3,5-trimethyl-6-(4-fluorophenyl)-cyclopentane[b]thiophene][2-(2,6-difluorophenyl)-2,3-dihydro-1H-indole-1-ylidene]titaniumamine (compound 21)

[0478]

[0479] Synthesized using the method described at the beginning of this section. Yield: 1.40 g (76%).

[0480] 1 H NMR (CDCl3, 400MHz): δ7.51-7.57(m,1H),7.41-7.49(m,4H),7.34-7.41(m,1H),7.19-7.29(m,2H),6.94 (t,J=8.8Hz,3H),4.86(d,J=17.5Hz,1H),4.71(d,J=17.5Hz,1H),2.44(s,3H),2.13(s,3H),2.09(s,3H). 1.5.4.Dichloro(eta 5 Synthesis of 2,3,5-trimethyl-6-isopropylcyclopentane[b]thiophene)[2-(2,6-difluorophenyl)-2,3-dihydro-1H-isoindole-1-ylidene]titaniumamine (compound 22)

[0481]

[0482] Use the method described at the beginning of this section for synthesis.

[0483] Yield: 616 mg (78%).

[0484] 1 H NMR (CDCl3, 400MHz): δ7.62-7.67(m,1H),7.53-7.58(m,1H),7.42-7.48(m,2H),7.27-7.36(m,1H),6.97-7.08(m,2H),6.26(s,1H),4.97(d,J=17 .3Hz,1H),4.70(d,J=17.4Hz,1H),2.92(sept,J=6.9Hz,1H),2.24(s,3H),2.04(s,3H),1.93(s,3H),1.02(d,J=6.9Hz,3H),0.89(d,J=6.9Hz,3H).

[0485] 1.6. Synthesis of titanium dimethylamidinyl complexes with cyclic and acyclic amidine groups.

[0486] The dichloride complex was suspended in diethyl ether (20 mL / mmol). The reaction mixture was cooled to -30 °C, and then MeMgBr (2.2 equivalents) was added. The mixture was stirred overnight at room temperature and then evaporated to dryness. Hexane (10 mL / mmol) was added to the residue, and the resulting suspension was filtered through a diatomaceous earth 503 pad. The filtrate was evaporated to dryness to give the dimethyltitanium complex. If desired, the product was recrystallized from n-pentane / n-hexane at -30 °C. The corresponding methyl compounds are indicated by the M suffix.

[0487] The following table reports the yield and 1H NMR characterization:

[0488]

[0489]

[0490]

[0491] Batch copolymerization was carried out in a 2-liter intermittent autoclave equipped with dual stirrers and baffles. The reaction temperature was set to 90 ± 3 °C (data shown in Tables 1, 2, 3, and 4) (120 ± 3 °C for the reactions in Table 5) and controlled using a Lauda thermostat. As is known to those skilled in the art, the feed stream (solvent and monomer) was purified by contact with various adsorption media to remove catalyst-killing impurities such as water, oxygen, and polar compounds. During polymerization, ethylene and propylene monomers were continuously fed into the reactor's gas cap. The reactor pressure was kept constant by a check valve.

[0492] In an inert nitrogen atmosphere, the reactor is filled with pentamethylheptane (PMH) (950 mL), MAO-10T (Crompton, 10 wt% toluene solution) or TiBA, BHT (2,6-di-tert-butyl-4-methylphenol), and for EPDM high ENB experiments, also 5-ethylidene-2-norbornene (ENB). The reactor is heated to 90 °C (or 120 °C, respectively) while stirring at 1350 rpm. The reactor is pressurized and regulated at a defined ethylene:propylene ratio, and for EPDM / EPDM high ENB experiments, additional hydrogen (0.35 NL / h) is added. After 15 minutes, the catalyst components and borate co-catalyst (if applicable) are added to the reactor (0.02–0.14 μmol, depending on catalyst yield), followed by flushing of the catalyst vessel with PMH (50 mL). After 10 minutes of polymerization, the monomer flow was terminated and the solution was carefully poured into a 2L Erlenmeyer flask containing a solution of Irganox-1076 in isopropanol, and dried under reduced pressure at 100°C overnight. The molecular weight (SEC-IR) and composition of the polymer were analyzed (FT-IR).

[0493] The experimental conditions and results are given at the bottom of the table.

[0494] 1. polymerization

[0495] Table 1: EPM 400 / 200NL / h; 90℃ 7 bar; MAO-10T

[0496] catalyst Catalyst dosage M-content C2 C3 Mn Mw Mw / Mn CE 1M 0.05 0.58 44.2 55.8 153 321 2.1 Compound 1M 0.07 0.27 51.3 48.7 309 661 2.1 Compound 2M 0.02 0.13 43.3 56.7 310 696 2.2 Compound 3M 0.07 0.66 48.9 51.1 205 398 1.9 Compound 4M 0.05 0.16 36.5 63.5 210 418 2.0 Compound 5M 0.05 0.28 36.5 63.5 202 383 1.9 Compound 7M 0.05 0.55 38.0 62.0 327 621 1.9 Compound 8M 0.02 0.15 47.3 52.7 408 809 2.0 Compound 9M 0.02 0.22 45.7 54.3 314 606 1.9 Compound 10M 0.05 0.83 48.3 51.7 301 609 2.0 Compound 11M 0.05 0.50 47.7 52.3 239 454 1.9 Compound 12M 0.02 0.15 45.2 54.8 337 620 1.8 Compound 13M 0.02 0.25 41.8 58.2 372 676 1.8 Compound 14M 0.02 0.11 45.1 54.9 386 758 2.0 Compound 16M 0.07 0.45 41.8 58.2 220 532 2.4 Compound 17M 0.07 0.57 40.2 59.8 314 661 2.1 Compound 18M 0.07 0.44 45.6 54.4 231 514 2.2 Compound 19M 0,03 0,5 36 64 264 573 2,2 Compound 20M 0,03 0,2 34 66 315 687 2,2 Compound 21M 0,03 0,3 32,1 67,9 272 581 2,1 Compound 22M 0,03 0,6 32,2 67,8 501 1074 2,1 Compound 23 0,05 0,41 49,1 50,9 180 403 2,2 Compound 24M 0,05 0,23 46,5 53,5 314 663 2,1 Compound 25M* 0.04 0.21 45.3 54.7 299 639 2.1 Compound 25M* 0.04 0.29 44.2 55.8 296 666 2.3

[0497] MAO-10T = 450 μmol / L; BHT / Al = 2; C3 = 400 Nl / h; C2 = 200 Nl / h; P = 7 bar; t = 10 minutes; T = 90°C

[0498] Table 2: EPM 400 / 200 NL / h; 90℃ 7 bar; TiBA / Triphenylmethyltetra(pentafluorophenyl)borate (TBF20)

[0499]

[0500]

[0501] TiBA = 450 μmol / L; BHT / Al = 2; Triphenylmethyltetra(pentafluorophenyl)borate B / Ti = 2; C3 = 400 Nl / h; C2 = 200 Nl / h; P = 7 bar; t = 10 minutes; T = 90 °C

[0502] Table 3: EPM 250 / 250NL / h; 90℃ 7 bar; MAO-10T + small amount of TiBA / borate

[0503]

[0504] MAO-10T = 450 μmol / L; BHT / Al = 2; C3 = 250 Nl / h; C2 = 250 Nl / h; P = 7 bar; t = 10 minutes; T = 90 °C

[0505] Table 4: EPDM 400 / 200NL / h high ENB; 90℃ 7 bar; MAO-10T

[0506]

[0507] MAO-10T = 450 μmol / L; BHT / Al = 2; C3 = 400 Nl / h; C2 = 200 Nl / h; H2 = 0.35 Nl / h; ENB = 2.8 ml; P = 7 bar; t = 10 minutes; T = 90 °C

[0508] *TiBA = 450 μmol / L; BHT / Al = 2; Triphenylmethyltetra(pentafluorophenyl)borate B / Ti = 2, instead of MAO-10T = 450 μmol / L;

[0509] Table 5: EPM 400 / 172NL / h, 120℃, 7.4 bar; TiBA / triphenylmethyltetra(pentafluorophenyl)borate

[0510]

[0511]

[0512] TiBA = 450 μmol / L; BHT / Al = 1; Triphenylmethyltetra(pentafluorophenyl)borate B / Ti = 2; C3 = 400 Nl / h; C2 = 172 Nl / h; P = 7.4 bar; t = 10 minutes; T = 120℃.

Claims

1. A metal complex of formula (1) TCyLMZ p (1), in M stands for titanium. Z is an anionic ligand, and Z is selected from C1-C4-alkyl groups. p is 2. TCy is a thiophene-fused cyclopentadienyl ligand of formula (2). in R 1 and R 2 Choose free hydrogen, halogen, and C1-C respectively. 10 Alkyl, C5-C 10 cycloalkyl, unsubstituted C6-C 10 Aryl, hydroxyl C1-C 10 -alkyl-substituted C6-C 10 aryl, C6-C substituted with C1-C4-dialkylamino 10 The group consists of aryl, SiR3, OR, NR2, SR, and PR2, where R represents C1-C respectively. 10 -alkyl, C5-C 10 -Cycloalkyl, C6-C 10 -Aryl, hydroxyC1-C 10 -alkyl-substituted C6-C 10 -aryl and C6-C substituted with C1-C4-dialkylamino groups 10 -Aryl, or R 1 R 2 It forms an aliphatic C5-C6 cyclic olefin ring with the two carbon atoms of the double bond in the thiophene ring. This cyclic olefin ring can be unsubstituted or substituted with C1-C4 alkyl groups. R 3 R 4 and R 5 Select free hydrogen, C1-C4 alkyl, and unsubstituted C6-C respectively. 10 -aryl, C6-C substituted with C1-C4-alkyl 10 -Aryl, halogenated C6-C 10 -Aryl, halogenated and C1-C4-alkyl substituted C6-C 10 -A group consisting of aryl, SiR3, OR, NR2, SR, and PR2, where R is selected freely from C1-C1. 10 -alkyl, C5-C 10 -Cycloalkyl, unsubstituted C6-C 10 -Aryl, hydroxyC1-C 10 -alkyl-substituted C6-C 10 -aryl and C6-C substituted with C1-C4-dialkylamino groups 10 -A group consisting of aryl groups, and L is the amidine ligand of formula (3a) In formula (3a), the amidine-containing ligand L is via the imine nitrogen atom N. 2 Covalently bonded to metal M, The benzo[a]ring fused with the amidine ring can be unsubstituted or may contain additional substituents R. 7 These substituents have an index "q", are selected from the group consisting of hydrogen, C1-C4-alkyl and halogen, and thus q is a number from 0 to 4. Sub4 is an unsubstituted phenyl group or a phenyl group substituted with one or more substituents selected from the group consisting of Cl, F and C1-C4-alkyl groups.

2. The metal complex according to claim 1, wherein TCy is a thiophene-fused cyclopentadienyl ligand of formula (2a). in n is a number between 3 and 4, and R 6 For each index m, it refers to C1-C4-alkyl. m is a number from 0 to 4.

3. A catalyst system comprising... a) The metal complex according to claim 1, b) An activator selected from the group consisting of boranes, borates, or organoaluminum compounds.

4. A method for preparing a polymer by polymerizing at least one olefinic monomer, the method comprising contacting the monomer with a metal complex according to claim 1 or a catalyst system according to claim 3, wherein ethylene, at least one C 3- C 12 -α-olefins and at least one non-conjugated diene selected from the group consisting of 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornediene, bicyclopentadiene and vinylcyclohexene are used as olefinic monomers.

5. The method according to claim 4, wherein TCy is a thiophene-fused cyclopentadienyl ligand of formula (2a). in n is a number between 3 and 4, and R 6 For each index m, it refers to C1-C4-alkyl. m is a number from 0 to 4.

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