Metal complex with a lewis base ligand

Abstract

A metal complex of the formula (1)
CyAMX(L).sub.n(1) wherein Cy is a cyclopentadienyl-type ligand, M is a metal of group 4; A is an amidine-containing ligand moiety, represented by formula 2: ##STR00001## wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom, and Sub1 is a substituent comprising a group 14 atom through which Sub1 is bonded to the imine carbon atom and Sub2 is a substituent comprising a heteroatom of group 15, through which Sub2 is bonded to the imine carbon atom; X is an allyl borate ligand derived from a conjugated diene ligand, D, and a borane, B and L is a neutral Lewis basic ligand wherein the number of said metal ligands n is in the range of 1 to the amount that specifies the 18-electron rule.

Claims

1. A metal complex of the formula (1)
CyAMX(L).sub.n(1) wherein: Cy is a cyclopentadienyl-type ligand; M is a metal of group 4; A is an amidine-containing ligand moiety, represented by formula 2: ##STR00006## wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom, and Sub1 is a substituent comprising a group 14 atom through which Sub1 is bonded to the imine carbon atom and Sub2 is a substituent comprising a heteroatom of group 15, through which Sub2 is bonded to the imine carbon atom; X is an allyl borate ligand derived from a conjugated diene ligand and a borane; and L is a neutral Lewis basic ligand and n is 1 to an amount that specifies the 18-electron rule.

2. The metal complex according to claim 1, wherein L is an ether, a thioether, an amine, a tertiary phosphane, an imine, a nitrile, are isonitrile, or a bi- or oligodentate donor.

3. The metal complex according to claim 1 wherein L is t-butylisonitrile.

4. The metal complex according to claim 1 wherein M is titanium.

5. The metal complex according to claim 1 wherein n is 1 or 2.

6. The metal complex according to claim 1, wherein X is an allyl borate ligand derived from a diene with a borane of the general formula BQ.sub.1Q.sub.2Q.sub.3 wherein Q.sub.1, Q.sub.2, and Q.sub.3 are individually a halogen atom, hydrocarbon group, halogenated hydrocarbon group, substituted silyl group, alkoxy group or di-substituted amino group.

7. The metal complex according to claim 1, wherein Sub1 is a phenyl or substituted phenyl residue and Sub2 is an amino radical of the formula NR.sup.4R.sup.5 with R.sup.4 and R.sup.5 being individually selected from the group of aliphatic hydrocarbyl, halogenated aliphatic hydrocarbyl, aromatic hydrocarbyl, and halogenated aromatic hydrocarbonyl residues, one of R.sup.4 and R.sup.5 may optionally form a heterocyclic structure with the other of R.sup.4 and R.sup.5, or with Sub1.

8. Process for manufacturing the metal complex according to claim 1, the process comprising reacting a metal complex of the formula (3)
CyAMX(3) with a Lewis base L.

9. The process according to claim 8, further comprising forming the metal complex of formula (3) by reacting a borane and a metal complex of formula (4)
CyAMD(4) wherein D is a conjugated diene.

10. A catalyst system comprising: a) the metal complex according to claim 1; and b) a scavenger.

11. The catalyst system according to claim 10, wherein the scavenger b) is a hydrocarbyl of a metal or metalloid of any of groups 1-13 or its reaction products with at least one sterically hindered compound containing a group 15 or 16 atom.

12. A process for preparing a polymer, the process comprising contacting at least one olefinic monomer with the catalyst according to claim 1 to polymerize the monomers.

13. A process for preparing a polymer, the process comprising contacting at least one olefinic monomer with the catalyst system according to claim 10 to polymerize the monomers.

14. The process according to claim 12, wherein the at least one olefinic monomer comprises ethylene and at least a C.sub.3-C.sub.12--olefin.

15. The process according to claim 12, wherein the at least one olefinic monomer comprises ethylene, at least one C.sub.3-12 alpha olefin, and at least one non-conjugated diene.

16. The process according to claim 15, wherein the at least one non-conjugated diene is a diene selected from the group consisting of 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornadiene, dicyclopentadiene, and vinylcyclohexene.

17. The metal complex according to claim 1, wherein; L is t-butylisonitrile; M is titanium; n is or 2; X is an allyl borate ligand derived from a dims with a borane of the general formula BQ.sub.1Q.sub.2Q.sub.3 wherein B is borane, and Q.sub.1, Q.sub.2, and Q.sub.3 are individually a halogen atom, hydrocarbon group, halogenated hydrocarbon group, substituted silyl group, alkoxy group or di-substituted amino group, and they may be the same or different; and Sub1 is a phenyl or substituted phenyl residue and Sub2 is an amino radical of the formula NR.sup.4R.sup.5 with R.sup.4 and R.sup.5 being individually selected from the group of aliphatic hydrocarbyl, halogenated aliphatic hydrocarbyl, aromatic hydrocarbyl, halogenated aromatic hydrocarbonyl residues, and one of R.sup.4 or R.sup.5 optionally forms a heterocyclic structure with the other of R.sup.4 or R.sup.5, or with Sub1.

18. The metal complex according to claim 1, wherein the borane is selected from the group consisting of 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-trifluoro-phenyl)-borane, phenylbis(pentafluorophenyl)borane, and tris(pentafluoro-phenyl)-borane (B(C.sub.6F.sub.5).sub.3).

Description

FIGURES

(1) FIG. 1 shows the X-ray structure of compound 3 of example 1

(2) FIG. 2 shows the X-ray structure of compound 2 of example 2

SYNTHESIS OF COMPOUNDS FOR THE COMPARATIVE EXAMPLES

(3) Cp*Ti{NC(Ph)N.sup.iPr.sub.2}(-1,4-C.sub.4H.sub.4Me.sub.2) (Compound A) was prepared as described for compound 3 in WO2011076772 and WO2011076775.

Synthesis of Cp*Ti{NC(Ph)(iPr2N)}Me2 (Compound B)

(4) To a stirring toluene (15 mL) solution of Cp*Ti{NC(Ph)N.sup.iPr.sub.2}Cl.sub.2 (3) (1.00 g, 2.20 mmol) was added dropwise MeLi (2.80 mL, 1.6 M in Et.sub.2O, 4.40 mmol) and the resulting solution was stirred for 16 h. The volatiles were then removed in vacuo and the yellow solid was then extracted into n-hexanes (50 mL). Concentration of the solution to ca 15 mL and subsequent storage at 30 C. for 24 h resulted in crystallisation of the desired product as large yellow crystals which were isolated and dried in vacuo. Yield=0.37 g (40%). The product was characterized by .sup.1H-NMR and .sup.13C-NMR.

Synthesis of Compounds for the Examples of the Invention

Synthesis of Cp*Ti{NC(Ph)NiPr2}{3-CH2C(Me)C(Me)CH2BArF3} (Compound 1)

(5) To a solution of Cp*Ti{NC(Ph)N.sup.iPr.sub.2}(-2,3-C.sub.4H.sub.4Me.sub.2) (0.30 g, 0.64 mmol) in toluene (20 mL) was added BAr.sup.F.sub.3 (0.33 g, 0.64 mmol) in toluene (20 mL). After ca. 30 s the solution changed to a darker colour. It was stirred for a further 2 h and the volatiles were removed in vacuo. The resulting green solid was washed with pentane (315 mL) and dried in vacuo. Yield=0.51 g (81%). The product was characterized by 1H-NMR and .sup.13C-NMR.

Synthesis of Cp*Ti{NC(Ph)NiPr2}{3-Et(CH)3CH2BArF3} (Compound 2)

(6) To a solution of Cp*Ti{NC(Ph)N.sup.iPr.sub.2}(-1,4-C.sub.4H.sub.4Me.sub.2) (Compound A) (0.30 g, 0.64 mmol) in toluene (20 mL) was added BAr.sup.F.sub.3 (0.33 g, 0.64 mmol) in toluene (20 mL). After ca. 30 seconds the solution changed to a darker green colour. It was stirred for a further 2 h and the solvent was removed in vacuo. The resulting green solid was washed with pentane (315 mL), dried in vacuo. Yield=0.58 g (93%). The product was characterized by .sup.1HHNR and .sup.13CNMR.

Example 1

Synthesis of Cp*Ti{NC(Ph)NiPr2}{3-CH2C(Me)C(Me)CH2BArF3}(tBuNC) (Compound 3)

(7) To a solution of Cp*Ti{NC(Ph)N.sup.iPr.sub.2}{.sup.3-CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3} (Compound 1) (0.50 g, 0.51 mmol) in toluene (15 mL) was added t-BuNC (57.7 L, 0.51 mmol). The solution immediately turned from green to dark red. After addition of n-hexanes (5 mL) the solution was left to stand for 16 h resulting in crystallisation of a red solid which was isolated, washed with n-hexanes (310 mL) and dried in vacuo. Yield=0.39 g (72%). Single crystals suitable for X-ray diffraction were grown from a toluene/n-hexanes solution at RT. Compound 3 can be stored in air for days without undergoing noticeable decomposition. The compound exists as a mixture of diastereomers in solution at 243 K: 3A and 3B in a ratio 60:40.

(8) Common data: .sup.19F NMR (Toluene-d.sub.8, 282.2 MHz, 293 K): 130.1 (br m, o-F, 6F), 164.2 (br m, p-F, 3F), 167.4 (br m, m-F, 8F) ppm. .sup.11B NMR (Toluene-d.sub.6, 96.2 MHz, 293 K): 13.4 ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 2171 (a, u(CN)), 1640 (w), 1617 (w), 1510 (m), 1419 (s), 1153 (s), 1075 (s), 1033 (w), 971 (s), 888 (m), 843 (m), 789 (w). Anal. found (calcd. for C.sub.52H.sub.53BF.sub.15N.sub.3Ti): C, 58.54 (58.72); H, 4.92 (5.02); N, 3.65 (3.95) %. EI-MS: m/z=512 (100%, [B(C.sub.6F.sub.5).sub.3].sup.+), 203 (100%, [NC(Ph)N.sup.iPr.sub.2].sup.+), 100 (100%, [N.sup.iPr.sub.2].sup.+).

(9) Data for 3A: .sup.1H NMR (CD.sub.2Cl.sub.2, 299.9 MHz, 243 K): 7.42-6.88 (5H, series of overlapping m, C.sub.6H.sub.5), 4.68 (1H, sept, CHMe.sub.2 cis to C.sub.6H.sub.5, .sup.3J=6.9 Hz), 3.46 (1H, br m, CHMe.sub.2 trans to C.sub.6H.sub.5), 2.36 (1H, app d, CH.sub.2BAr.sup.F.sub.3, .sup.2J=9.8 Hz), 2.05 (3H, s, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 1.91 (1H, d, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3, .sup.2J=7.2 Hz), 1.71 (9H, s, .sup.tBuNC), 1.55 (15H, s, C.sub.5Me.sub.5), 1.48 (3H, s, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.2), 1.20 (3H, d, CHMe.sub.2, trans to C.sub.6H.sub.5, .sup.3J=6.5 Hz), 1.12 (3H, d, CHMe.sub.2 trans to C.sub.6H.sub.5, .sup.3J=6.5 Hz), 1.02 (3H, d, CHMe.sub.2 cis to C.sub.6H.sub.5, .sup.3J=6.9 Hz), 0.91 (3H, d, CHMe.sub.2 cis to C.sub.6H.sub.5, .sup.3J=6.9 Hz), 0.87 (1H, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3 (overlapping with CHMe.sub.2 of 3B)), 0.27 (1H, app d, .sup.2J=9.8 Hz, CH.sub.2BAr.sup.F.sub.3) ppm. 13C-{.sup.1H} NMR (CD.sub.2Cl.sub.2, 75.4 MHz, 293 K): 160.9 (NC(Ph)N.sup.iPr.sub.2), 147.8 (C.sub.6F.sub.5), 147.4 (.sup.tBuNC), 139.5 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 138.7 (C.sub.6F.sub.5), 136.2 (i-C.sub.6H.sub.5), 135.5 (C.sub.6F.sub.5), 129.1 (o or m-C.sub.6H.sub.5), 128.3 (m- or o-C.sub.6H.sub.6), 126.4 (p-C.sub.6H.sub.5), 123.9 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 118.9 (C.sub.5Me.sub.5), 74.3 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 58.6 (CMe.sub.3), 53.3 (CHMe.sub.2 trans to C.sub.6H.sub.5), 47.0 (CHMe.sub.2 cis to C.sub.6H.sub.5), 30.3 (CMe.sub.3), 25.5 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 22.3 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 21.7 (CHMe.sub.2, trans to C.sub.6H.sub.5), 21.5 (CHMe.sub.2 trans to C.sub.6H.sub.6), 21.4 (CHMe.sub.2, cis to C.sub.6H.sub.6), 19.9 (CHMe.sub.2 cis to C.sub.5H.sub.5), 11.9 (C.sub.5Me.sub.5) ppm (CH.sub.2BAr.sup.F.sub.3 and i-C.sub.6F.sub.5 were not observed).

(10) Data for 3B: .sup.1H NMR (CD.sub.2Cl.sub.2, 299.9 MHz, 243 K): 7.42-6.88 (5H, series of overlapping m, C.sub.6H.sub.5), 3.39 (2H, sept, CHMe.sub.2, .sup.3J=7.1 Hz), 2.17 (1H, d, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3, .sup.2J 5.5 Hz), 2.01 (1H, app d, CH.sub.2BAr.sup.F.sub.3, .sup.2J=11.7 Hz), 1.86 (3H, s, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 1.83 (15H, a C.sub.5Me.sub.5), 1.68 (3H, s, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 1.30 (9H, s, .sup.tBuNC), 1.23 (1H, CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3 (overlapping with CHMe.sub.2 of 3A)), 0.85 (6H, d, CHMe.sub.2, .sup.3J=7.5 Hz), 0.81 (6H, d, CHMe.sub.2, .sup.3J=6.6 Hz), 0.38 (1H, app d, .sup.2J=11.7 Hz, CH.sub.2BAr.sup.F.sub.3) ppm. .sup.13C-{.sup.1H} NMR (CD.sub.2Cl.sub.2, 75.4 MHz, 293 K): 164.0 (NC(Ph)N.sup.iPr.sub.2), 147.2 (.sup.tBuNC), 138.9 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 136.3 (i-C.sub.6H.sub.5), 129.2 (o- or m-C.sub.6H.sub.6), 129.0 (o- or m-C.sub.6H.sub.5), 127.9 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 125.4 (p-C.sub.6H.sub.5), 118.4 (C.sub.5Me.sub.5), 70.8 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 57.8 (CMe.sub.3), 46.9 (CHMe.sub.2), 29.6 (CMe.sub.3), 24.6 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.2), 24.0 (CHMe.sub.2), 22.2 (CH.sub.2C(Me)C(Me)CH.sub.2BAr.sup.F.sub.3), 12.3 (C.sub.5Me.sub.5) ppm (CH.sub.2BAr.sup.F.sub.3 and i-C.sub.6F.sub.5 were not observed; other C.sub.6F.sub.5 resonances could not be distinguished from those of 3A)

Example 2

Synthesis of Cp*Ti{NC(Ph)NiPr2}{3-Et(CH)3CH2BArF3}(tBuNC) (Compound 4)

(11) To a solution of Cp*Ti{NC(Ph)N.sup.iPr.sub.2}{.sup.3-Et(CH).sub.3CH.sub.2BAr.sup.F.sub.3} (Compound 2) (0.50 g, 0.51 mmol) in toluene (15 mL) was added .sup.tBuNC (57.7 L, 0.51 mmol). The solution immediately turned from green to dark red and on standing at RT for 3 h, dark red crystals of Compound 4 had grown. These were isolated, washed with n-hexanes (310 mL), and dried in vacuo. Yield=0.42 g (77%). Compound 4 can be stored in air for days without undergoing noticeable decomposition. .sup.1H NMR (CD.sub.2Cl.sub.2, 499.9 MHz, 293 K): 7.35-6.97 (5H, series of m, C.sub.6H.sub.5), 4.44 (1H, dd, EtCHCH, .sup.3J=13.9 Hz, 15.8 Hz), 3.53 (2H, br m, CHMe.sub.2), 3.08 (1H, app d, CH.sub.2BAr.sup.F.sub.3, .sup.2J=10.3 Hz), 2.39 (1H, m, CHCH.sub.2BAr.sup.F.sub.3), 1.91 (1H, app d, CH.sub.2BAr.sup.F.sub.3, .sup.2J=10.3 Hz), 1.78 (1H, m, CHEt), 1.69 (15H, s, C.sub.5Me.sub.5), 1.60 (9H, s, .sup.tBuNC), 1.46 (2H, br m, CH.sub.2Me), 1.27 (6H, br d, CHMe.sub.2), 0.97 (6H, d, CHMe.sub.2, .sup.3J 7.8 Hz), 0.81 (3H, t, CH.sub.2Me, .sup.3J=8.2 Hz) ppm. .sup.13C-{.sup.1H} NMR (CD.sub.2Cl.sub.2, 125.8 MHz, 293 K): 164.0 (NC(Ph)N.sup.iPr.sub.2), 148.8 (C.sub.6F.sub.5), 138.9 (.sup.tBuNC), 138.7 (C.sub.6F.sub.5), 138.6 (i-C.sub.6H.sub.5), 136.9 (C.sub.6F.sub.5), 129.6 (o- or m-C.sub.6H.sub.5), 129.1 (m- or o-C.sub.6H.sub.5), 128.8 (p-C.sub.5H.sub.5), 125.8 (CHCH.sub.2BAr.sup.F.sub.2), 124.8 (EtCHCH), 118.9 (C.sub.5Me.sub.5), 92.2 (CHEt), 58.9 (CMe.sub.3), 48.1 (CHMe.sub.2), 33.0 (CH.sub.2BAr.sup.F.sub.3), 31.5 (CH.sub.2Me), 30.5 (CMe.sub.3), 21.7 (CHMe.sub.2), 21.3 (CHMe.sub.2), 19.1 (diene CH.sub.2Me), 12.0 (C.sub.5Me.sub.5) ppm (i-C.sub.6F.sub.5 was not observed). .sup.19F NMR (Toluene-d.sub.8, 282.2 MHz, 293 K): 131.3 (m, o-F, 6F), 162.8 (m, p-F, 3F), 166.3 (m, m-F, 6F) ppm. .sup.11B NMR (Toluene-d.sub.6, 96.2 MHz, 293 K): 12.3 ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 2177 (s, u(CN)), 1509 (s), 1331 (s), 1269 (s), 1194 (m), 1158 (m), 1136 (m), 1076 (s), 1026 (w), 918 (m), 885 (w), 789 (w), 758 (w), 726(s), 571 (m). Anal. found (calcd. for C.sub.52H.sub.53BF.sub.15N.sub.3Ti): C, 58.56 (58.72); H, 5.16 (5.02); N, 3.73 (3.95) %. EI-MS: m/z=512 (100%, [B(C.sub.6F.sub.5).sub.3].sup.+), 494 (10%, [M-B(C.sub.6F.sub.5).sub.3-.sup.tBu].sup.+), 83 (80%, [.sup.tBuNC].sup.+), 57 (100%, [N.sup.iPr].sup.+). Single crystals suitable for X-ray diffraction were grown from a toluene/n-hexanes solution at room temperature.

Polymerization Example

Batch EPDM Copolymerisation (General Process)

(12) The batch copolymerizations were carried out in a 2-liter batch autoclave equipped with a double intermig and baffles. The reaction temperature was set on 90 C. and controlled by a Lauda Thermostat. The feed streams (solvents and monomers) were purified by contacting with various adsorption media to remove catalyst killing impurities such as water, oxygen and polar compounds as is known to those skilled in the art. During polymerisation the ethylene and propylene monomers were continuously fed to the gas cap of the reactor. The pressure of the reactor was kept constant by a back pressure valve.

(13) In an inert atmosphere of nitrogen, the reactor was filled with pentamethyl heptanes (PMH) (950 mL), Isobutylaluminoxane (IBAO-65, 13 wt %, hexane solutions; Akzo Nobel, 3.5 wt % Al in n-hexanes), BHT, 5-ethylidene-2-norbornene (ENB) (0.7 mL) and 5-vinyl-2-norbornene (VNB) (0.7 mL). The reactor was heated to 90 C., while stirring at 1350 rpm. The reactor was pressurized and conditioned under a determined ratio of ethylene, propylene and hydrogen (0.35 NL/h) After 15 minutes, the catalyst components were dosed under inert conditions as toluene or n-hexanes solutions into the reactor and the catalyst vessel was rinsed with PMH (50 mL) subsequently. (When B(C.sub.6F.sub.5).sub.3 was used; the borane was added directly after the catalyst was added. This was activation via abstraction of the .sup.tBuNC ligand in the case of Compound 4 and activation via abstraction of the methyl and diene ligands in the cases of Compounds B and D). After 10 minutes of polymerisation, the monomer flow was stopped and the solution was carefully dumped in an Erlenmeyer flask of 2 L, containing a solution of Irganox-1076 in isopropanol and dried over night at 100 C. under reduced pressure. The polymers were analysed for molecular weight distribution (SEC-DV) and composition (FT-IR).

(14) The experimental conditions and results are given in table 1.

(15) TABLE-US-00001 TABLE 1 Metal-organic Equivs of Residual Organo- compound Added Ti in Incorporated metallic IBAO dosage B(C.sub.5F.sub.5).sub.3 Yield polymer C2 ENB VNB Mw Example Compound (mol) (mol) Cocal. (g) (ppm).sup.1 (wt %) (wt %) (wt %) (kg/mol) Mw/Mn 1 4 450 0.14 0 5.31 1.26 54.0 1.03 0.72 125 2.1 2 4 450 0.14 1 8.85 0.76 48.9 0.99 0.67 5 A 450 0.14 0 0.88 7.62 6 A 450 0.14 1 8.0 0.84 53.0 1.09 0.75 120 2.4 9 B 450 0.14 0 3.10 2.16 10 B 450 0.14 1 7.49 0.89 53.4 0.96 0.66 100 2.6 [BHT]/[Al] = 2 mol/mol; C3 feed = 400 NL/h; C2 feed = 200 NL/h; ENB feed = 0.7 ml; VNB feed = 0.7 ml; H2 feed = 0.35 NL/h T = 90 C.; P = 7 barg .sup.1Calculated value