Synthesis of Ethylene-Bridged Bis(indenyl) Zirconium, Hafnium Complexes and Their Catalytic Behavior on Selective Propylene Oligomerization: the Effect of 3-Substituent on Indenyl Ring

doi:10.6023/A23050258

Abstract

Oligomerization of propylene or other α-olefins is the main way to obtain various branched α-olefins, which are potential comonomers for the preparation of novel polymers with excellent properties or building blocks for manufacturing fine chemicals. Due to the different coordination-insertion and chain transfer modes involved in the oligomerization process of propylene, propylene oligomers with different structures were generally obtained, thus developing novel catalysts capable of catalyzing selective propylene oligomerization attracts great attention. In this work, a series of novel ethylene-bridged bis(indenyl) complexes meso-/rac-1~7 [ansa-C₂H₄-(3-R-4,7-Me₂-C₉H₃)₂MCl₂: M=Zr, R=ⁿBu (meso-/rac-1), ⁱPr (meso-2), CH₂Cy (meso-/rac-3), Bn (meso-/rac-4), CH₂C₆H₄(4-CH₃) (meso-/rac-5); M=Hf, R=CH₂C₆H₄(4-CH₃) (meso-/rac-7); ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-(CH₂)₃]C₉H₂}₂ZrCl₂ (meso-6)] were synthesized via the reaction of the dilithium salts of the proligands with 1 equiv. of ZrCl₄ or HfCl₄ in Et₂O, and in most of the cases, both the rac- and meso-isomers were separated in analytically pure forms via recrystallization. All complexes were characterized by nuclear magnetic resonances (¹H NMR, ¹³C NMR) and elemental analysis (EA) methods. The molecular structures of typical complexes rac-1, meso-1, meso-2, meso-4, meso-5 and meso-6 were further determined by X-ray single crystal diffraction studies. The solid-state molecular structures of these complexes exhibit essentially similar geometrical parameters. The bond lengths between zirconium center and carbon atoms of the π-bonding five-membered ring of the indenyl unit vary slightly, suggesting a η⁵-coordination mode of the five-membered rings. In the presence of methylaluminoxane (MAO) as the cocatalyst, zirconium complexes meso-/rac-1~3 with an alkyl group on the 3-position of the indenyl ring catalyzed the oligomerization of propylene with high activities up to 9.73×10⁶ g•mol-Zr^－1•h^－1, affording propylene oligomers with molecular weights of hundreds to thousands. Meanwhile, meso-/rac-1~3 exhibited low selectivities for β-Me elimination, with the highest allyl end group content being 41.3%. Zirconium and hafnium complexes meso-/rac-4~7 with a benzyl group or a substituted benzyl group on the 3-position of the indenyl ring were found to catalyze the dimerization of propylene in the presence of MAO, and mixtures including 1-pentene, 2-methyl-1-pentene, 4-methyl-1-pentene, 2,4-dimethyl-1-pentene were obtained. Temperature is the major factor affecting the activities of dimerization, and among them complex rac-4 showed the highest activity of 1.24×10⁶ g•mol-Zr^－1•h^－1 at 80 ℃. The distribution of dimers is hardly affected by the reaction temperature or the Al/Zr molar ratio adopted. Among them, the hafnium complex rac-7 showed the highest β-Me elimination selectivity up to 60.1%.

Key words: metallocene, catalyst, propylene, oligomerization, dimerization

Cite this article

Bo Li, Haiyan Zhou, Haiyan Ma, Jiling Huang. Synthesis of Ethylene-Bridged Bis(indenyl) Zirconium, Hafnium Complexes and Their Catalytic Behavior on Selective Propylene Oligomerization: the Effect of 3-Substituent on Indenyl Ring[J]. Acta Chimica Sinica, 2023, 81(10): 1280-1294.

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Complex	α/(°)	β/(°)	Zr—Cent/nm
rac-1	125.76	61.10	0.2227, 0.2231
meso-1	125.81	59.96	0.2215, 0.2223
meso-2	124.82	65.37	0.2227, 0.2235
meso-4	124.21	64.60	0.2231, 0.2238
meso-5	125.75	61.37	0.2218, 0.2211
meso-6	127.68	58.08	0.2235, 0.2235

Complex	α/(°)	β/(°)	Zr—Cent/nm
rac-1	125.76	61.10	0.2227, 0.2231
meso-1	125.81	59.96	0.2215, 0.2223
meso-2	124.82	65.37	0.2227, 0.2235
meso-4	124.21	64.60	0.2231, 0.2238
meso-5	125.75	61.37	0.2218, 0.2211
meso-6	127.68	58.08	0.2235, 0.2235

Run	Cat.	T_p/℃	Yield/g	Act./(10⁶ g•mol-Zr^－1•h^－1)	M_n^b/(g•mol^－1)	Ally content^c/%
1	meso-1	40	2.046	3.27	854	18.4
2		60	3.165	5.06	543	16.1
3		80	4.732	7.57	327	15.7
4		100	2.803	4.48	254	13.3
5	meso-2	40	1.932	3.09	846	30.2
6		60	3.016	4.83	631	26.5
7		80	3.612	5.78	492	23.1
8		100	2.547	4.08	316	22.8
9	meso-3	40	1.124	1.80	1032	41.3
10		60	2.011	3.22	823	36.5
11		80	2.932	4.69	535	28.1
12		100	1.773	2.84	383	26.4
13	rac-1	40	3.146	5.03	1764	18.7
14		60	3.761	6.02	1235	15.9
15		80	5.312	8.50	824	14.3
16^d		80	Trace	—	—	—
17^e		80	Trace	—	—	—
18		100	6.083	9.73	365	13.6
19	rac-3	40	2.996	4.79	2242	40.5
20		60	3.542	5.67	1536	35.9
21		80	4.132	6.61	941	28.3
22		100	5.547	8.88	447	25.7

Run	Cat.	T_p/℃	Yield/g	Act./(10⁶ g•mol-Zr^－1•h^－1)	M_n^b/(g•mol^－1)	Ally content^c/%
1	meso-1	40	2.046	3.27	854	18.4
2		60	3.165	5.06	543	16.1
3		80	4.732	7.57	327	15.7
4		100	2.803	4.48	254	13.3
5	meso-2	40	1.932	3.09	846	30.2
6		60	3.016	4.83	631	26.5
7		80	3.612	5.78	492	23.1
8		100	2.547	4.08	316	22.8
9	meso-3	40	1.124	1.80	1032	41.3
10		60	2.011	3.22	823	36.5
11		80	2.932	4.69	535	28.1
12		100	1.773	2.84	383	26.4
13	rac-1	40	3.146	5.03	1764	18.7
14		60	3.761	6.02	1235	15.9
15		80	5.312	8.50	824	14.3
16^d		80	Trace	—	—	—
17^e		80	Trace	—	—	—
18		100	6.083	9.73	365	13.6
19	rac-3	40	2.996	4.79	2242	40.5
20		60	3.542	5.67	1536	35.9
21		80	4.132	6.61	941	28.3
22		100	5.547	8.88	447	25.7

Run	Cat.	T_p/℃	Dimer^b/%				Dimer/mg	β-Me^c/%	Act./(10⁵ g•mol-M^－1•h^－1)
Run	Cat.	T_p/℃	1-P	4-M-1-P	2-M-1-P	2,4-M-1-P	Dimer/mg	β-Me^c/%	Act./(10⁵ g•mol-M^－1•h^－1)
1	meso-4	40	28.4	20.7	32.5	18.2	238	49.3	4.76
2		60	30.2	16.9	33.8	19.1	463	47.1	9.26
3		80	29.6	14.7	36.1	19.6	510	44.3	10.2
4		100	27.9	17.7	34.5	19.9	216	45.6	4.32
5	meso-5	40	33.4	19.2	35.7	11.6	224	52.6	4.48
6		60	31.7	16.3	37.6	14.4	436	48.0	8.72
7		80	33.5	16.1	36.1	14.3	454	49.6	9.08
8		100	27.6	20.4	35.2	16.8	196	48.0	3.92
9	meso-6	40	28.3	18.5	33.2	20.0	127	46.8	2.54
10		60	27.9	18.7	34.2	19.2	321	46.6	6.42
11		80	29.5	16.0	39.7	14.8	438	45.5	8.76
12		100	28.6	17.3	35.4	19.7	196	45.9	3.92
13	rac-4	40	29.7	19.2	32.9	18.2	259	48.9	5.18
14		60	34.2	15.4	33.5	16.9	487	49.6	9.73
15		80	29.7	16.3	39.9	14.1	620	46.0	12.4
16		100	29.4	18.6	34.2	17.7	231	48.0	4.62
17	rac-5	40	34.3	19.2	33.9	12.6	239	53.5	4.78
18		60	30.5	17.0	37.5	15.0	459	47.5	9.18
19		80	33.7	16.3	35.9	14.1	498	50.0	10.0
20		100	29.0	20.0	32.9	18.1	210	49.0	4.20
21	meso-7	40	33.8	24.5	22.6	19.1	28	58.3	0.56
22		60	32.7	25.3	24.2	17.8	51	58.0	1.02
23		80	33.3	26.8	21.1	18.3	71	60.1	1.42
24		100	31.8	24.9	23.6	19.7	49	56.7	0.98
25	rac-7	40	32.4	26.5	23.5	17.6	21	58.9	0.42
26		60	31.4	27.3	26.1	15.2	48	58.7	0.96
27		80	26.0	29.9	19.5	24.7	77	55.9	1.54
28		100	29.7	26.2	29.5	14.6	61	55.9	1.22

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