亚乙基桥联双茚锆、铪配合物的合成及催化丙烯选择性齐聚研究: 茚环3-位取代基的影响

doi:10.6023/A23050258

摘要/Abstract

设计并合成了12个亚乙基桥联双茚类锆、铪配合物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)]. 所有配合物均通过了核磁共振(¹H NMR、¹³C NMR)和元素分析(EA)的鉴定, 其中配合物rac-1、meso-1、meso-2、meso-4、meso-5和meso-6的空间结构进一步通过X射线单晶衍射确证. 在助催化剂甲基铝氧烷(MAO)存在下, 茚环3-位为烷基取代的锆配合物meso-/rac-1~3催化丙烯齐聚主要得到分子量为几百至几千的丙烯齐聚物, 活性最高可达9.73×10⁶ g•mol-Zr^－1•h^－1, 同时表现出较低的β-Me消除选择性, 齐聚产物烯丙基端基含量最高为41.3%. 茚环3-位为苄基或取代苄基的双茚锆、铪配合物meso-/rac-4~7催化丙烯齐聚主要得到丙烯二聚体, 为1-戊烯、2-甲基-1-戊烯、4-甲基-1-戊烯、2,4-二甲基-1-戊烯的混合物. 温度为影响丙烯二聚活性的主要因素, 其中配合物rac-4在80 ℃时催化丙烯二聚活性可高达1.24×10⁶ g•mol-Zr^－1•h^－1. 二聚物的分布受温度及Al/Zr比的影响不大. 铪配合物rac-7表现出较高的β-Me消除选择性, 最高可达60.1%.

关键词: 茂金属配合物, 催化剂, 丙烯, 齐聚, 二聚

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

引用此文

李波, 周海燕, 马海燕, 黄吉玲. 亚乙基桥联双茚锆、铪配合物的合成及催化丙烯选择性齐聚研究: 茚环3-位取代基的影响[J]. 化学学报, 2023, 81(10): 1280-1294.

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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参考文献 38

[1]	Rosenthal, U. ChemCatChem 2020, 12, 41. doi: 10.1002/cctc.v12.1
[2]	Sydora, O. L. Organometallics 2019, 38, 997. doi: 10.1021/acs.organomet.8b00799
[3]	Wang, M.; Wu, W.; Wang, X.; Huang, X.; Nai, Y.; Wei, X.; Mao, G. RSC Adv. 2020, 10, 43640. doi: 10.1039/D0RA07558B
[4]	Bekmukhamedov, G. E.; Sukhov, A. V.; Kuchkaev, A. M.; Yakhvarov, D. G. Catalysts 2020, 10, 498. doi: 10.3390/catal10050498
[5]	Titova, Y. Y.; Schmidt, F. K. Catalysts 2021, 11, 1489. doi: 10.3390/catal11121489
[6]	Olivier-Bourbigou, H.; Breuil, P. A. R.; Magna, L.; Michel, T.; Pastor, M. F. E. Chem. Rev. 2020, 120, 7919. doi: 10.1021/acs.chemrev.0c00076
[7]	Khamiyev, M.; Khanmetov, A.; Reza, V. A.; Aliyeva, R.; Hajıyeva-Atayi, K.; Akhundova, Z.; Khamiyeva, G. Appl. Organomet. Chem. 2020, 34, e5409.
[8]	Bryliakov, K. P.; Antonov, A. A. J. Organomet. Chem. 2018, 867, 55. doi: 10.1016/j.jorganchem.2018.03.021
[9]	Zhong, X.; Liu, Z. J. Mol. Catal. (Chin.) 2022, 36, 374 (in Chinese).
	(钟绪琴, 刘振, 分子催化, 2022, 36, 374.)
[10]	Wang, Y.; Liu, Y.; Han, Q.; Lin, H.; Liu, F. J. Membrane Sci. 2022, 649, 120359. doi: 10.1016/j.memsci.2022.120359
[11]	Sung, Y.; Huang, P.; Huang, S.; Chiang, Y.; Tsai, J. Polymers 2022, 14, 4815. doi: 10.3390/polym14224815
[12]	Wang, L.; Ni, X.; Ren, H.; Gao, Y.; Gao, H. Acta Polym. Sin. 2021, 52, 1481 (in Chinese).
	(王凌志, 倪兴强, 任鹤, 高宇新, 高海洋, 高分子学报, 2021, 52, 1481.)
[13]	Zhang, Y.; Tang, Y.; Guo, Z.; Jia, X.; Wang, W.; Li, H.; Jiang, Z. China Synth. Resin Plast. 2023, 40, 62 (in Chinese).
	(张垚, 唐毓婧, 郭子芳, 贾雪飞, 王伟, 李昊坤, 姜志勇, 合成树脂及塑料, 2023, 40, 62.)
[14]	Nelkenbaum, E.; Kapon, M.; Eisen, M. S. Organometallics 2005, 24, 2645. doi: 10.1021/om0490379
[15]	Dçtterla, M.; Alt, H. G. Adv. Synth. Catal. 2012, 354, 399. doi: 10.1002/adsc.v354.2/3
[16]	Svejda, S. A.; Brookhart, M. Organometallics 1999, 18, 65. doi: 10.1021/om980736t
[17]	Benvenuti, F.; Carlini, C.; Marchionna, M.; Maria, A.; Galletti, R.; Sbrana, G. J. Mol. Catal. A: Chem. 2002, 178, 9. doi: 10.1016/S1381-1169(01)00285-0
[18]	Zhao, W.; Qian, Y.; Huang, J.; Duan, J. J. Organomet. Chem. 2004, 689, 2614. doi: 10.1016/j.jorganchem.2004.05.021
[19]	Liu, L.; Liu, Z.; Cheng, R.; He, X.; Liu, B. Organometallics 2021, 40, 1682. doi: 10.1021/acs.organomet.1c00167
[20]	Lang, J. R.V.; Denner, C. E.; Alt, H. G. J. Mol. Catal. A: Chem. 2010, 322, 45. doi: 10.1016/j.molcata.2010.02.013
[21]	Janiak, C. Coordin. Chem. Rev. 2006, 250, 66. doi: 10.1016/j.ccr.2005.02.016
[22]	Eshuis, J. J. W.; Tan, Y. Y.; Teuben, J. H. J. Mol. Catal. 1990, 62, 277. doi: 10.1016/0304-5102(90)85223-5
[23]	Suzuki, Y.; Yasumoto, T.; Mashima, K.; Okuda, J. J. Am. Chem. Soc. 2006, 128, 13017. doi: 10.1021/ja063717g
[24]	Huang, W.; Wang, Y.; Ma, H.; Huang, J. Appl. Organomet. Chem. 2014, 10, 413.
[25]	Wang, Y.; Huang, W.; Ma, H.; Huang, J. Polyhedron 2014, 76, 81. doi: 10.1016/j.poly.2014.03.019
[26]	Zhang, L.; Zhang, B.; Ma, H. Chin. J. Polym. Sci. 2019, 37, 578. doi: 10.1007/s10118-019-2224-1
[27]	Zhang, L.; Ma, H. Acta. Chim. Sinica 2020, 78, 778 (in Chinese). doi: 10.6023/A20030092
	(张雷, 马海燕, 化学学报, 2020, 78, 778.)
[28]	Decker, P. J. W.; Hessen, B.; Teuben, J. H. Angew. Chem., Int. Ed. 2001, 40, 2516. doi: 10.1002/(ISSN)1521-3773
[29]	Suttil, J. A.; McGuinness, D. S.; Evans, S. J. Dalton Trans. 2010, 39, 5278. doi: 10.1039/c000913j
[30]	Tobisch, S.; Ziegler, T. J. Am. Chem. Soc. 2004, 126, 9059. doi: 10.1021/ja048861l
[31]	Tobisch, S.; Ziegler, T. Organometallics 2004, 23, 4077. doi: 10.1021/om0498100
[32]	Tobisch, S.; Ziegler, T. Organometallics 2005, 24, 256. doi: 10.1021/om049362w
[33]	Chen, E. Y.-X.; Marks, T. J. Chem. Rev. 2000, 100, 1391. doi: 10.1021/cr980462j
[34]	Busico, V.; Cipullo, R.; Cutillo, F.; Friederichs, N.; Ronca, S.; Wang, B. J. Am. Chem. Soc. 2003, 125, 12402. doi: 10.1021/ja0372412
[35]	Stapleton, R. A.; Galan, B. R.; Collins, S.; Simons, R. S.; Garrison, J. C.; Youngs, W. J. J. Am. Chem. Soc. 2003, 125, 9246. doi: 10.1021/ja030121+
[36]	Busico, V.; Cipullo, R.; Pellecchia, R.; Talarico, G.; Razavi, A. Macromolecules 2009, 42, 1789. doi: 10.1021/ma900066n
[37]	Zhou, Y.; Li, X. Y.; Xu, J. X.; Hou, S. L. J. Mol. Catal. A: Chem. 2012, 365, 203. doi: 10.1016/j.molcata.2012.09.005
[38]	Aitola, E.; Surakka, M.; Repo, T.; Linnolahti, M.; Lappalainen, K.; Kervinen, K.; Klinga, M.; Pakkanen, T.; Leskela, M. J. Organomet. Chem. 2005, 690, 773. doi: 10.1016/j.jorganchem.2004.09.089

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