不同配体的稀土金属配合物在烯烃聚合领域的研究进展

doi:10.6023/A23010004

摘要/Abstract

催化剂在推动聚烯烃工业发展中有着举足轻重的作用, 其中金属催化剂的设计与合成更是金属有机催化化学的关键. 稀土金属具有独特的轨道结构、反应活性和配位准则, 因此稀土金属配合物通过在金属中心周围引入空间位阻, 在聚烯烃材料制备中表现出独特优势. 其中配体是决定稀土金属配合物的结构、化学活性及稳定性等方面的关键因素. 本综述介绍了茂基配体(烷基取代、芳基取代、茚和芴配体)和非茂基配体(大环四齿配体、三齿配体、双齿配体和单齿配体)的稀土金属配合物的发展及其在聚烯烃制备中的应用. 这项工作旨在促进稀土金属催化剂在聚烯烃催化和金属有机催化领域的研究, 为高端化、差异化聚烯烃聚合催化剂的制备提供新的设计思路和研究方法.

关键词: 稀土金属配合物, 聚烯烃, 茂基配体, 非茂基配体

Catalysts play a pivotal role in promoting the development of polyolefin industry, especially, the design and synthesis of metal-catalysts is the key to the metal-organic chemistry. Surprisingly, rare-earth metal harness the unique orbital structure, reactivity and coordination criteria, so rare-earth metal complexes have been one of the efficient catalysts and show the special advantages in the preparation of polyolefin materials by introducing steric hindrance around the metal center, notably, their structure, chemical activity and stability are determined by ligands. The development of rare-earth metal catalysts with cyclopentadienyl ligands (alkyl-substituted, aryl-substituted, indenyl and fluorenyl ligands) and non-cyclopentadienyl ligands (macrocyclic tetradentate, tridentate, didentate, mondentate ligands), and their applications in the preparation of polyolefins are described in this review. This work aims to promote the research of rare-earth metal catalysts in the field of polyolefin synthesis and metal-organic catalysis, as well provide new design ideas and research methods for the synthesis of high-quality and functionalized polyolefin catalysts.

Key words: rare-earth organometallic complex, polyolefin, cyclopentadienyl ligand, non-cyclopentadienyl ligand

引用此文

汪阳, 阎敬灵. 不同配体的稀土金属配合物在烯烃聚合领域的研究进展[J]. 化学学报, 2023, 81(3): 275-288.

Yang Wang, Jingling Yan. Progress in Rare-earth Metal Complexes with Different Ligands in Olefin Polymerization[J]. Acta Chimica Sinica, 2023, 81(3): 275-288.

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图/表 24

图1. (C5Me5)2Sm(THF)n和(C5Me5)3Sm配合物的结构

Figure 1. The structures of the complexes (C5Me5)2Sm(THF)n and (C5Me5)3Sm

图2. (a) 烷烃消除反应合成单茂双烷基钇配合物的路线图. (b) 单茂双烷基钪配合物结构. (c) 单茂钇、镥相应氢化物结构

Figure 2. (a) The route of alkane elimination reaction for the synthesis of mono-metallocene bis-alkyl yttrium complexes. (b) The structures of mono-metallocene bis-alkyl scandium complexes. (c) The structures of mono-metallocene corresponding hydrides of yttrium and lutetium

图3. 限制几何构型(CGC)稀土配合物结构

Figure 3. The structures of constrained geometry configuration rare- earth complexes

图4. 杂环取代的环戊二烯稀土配合物结构

Figure 4. The structures of heterocyclic cyclopentadienyl rare-earth complexes

图5. (a) 双核桥连茂钪阳离子配合物体系的催化乙烯＋氨基-烯烃共聚. (b) 硅桥连的双环戊二烯基二价钐配合物催化聚合得到三嵌段共聚物. (c) 制备双核半三明治型单氯单烷基的钪金属配合物

Figure 5. (a) Catalytic copolymerization of ethylene＋amino-olefin with dinuclear bridged scandium cationic complex system. (b) Catalytic polymerization of silicon-bridged dicyclopentadienyl divalent samarium complex to obtain triblock copolymer. (c) The scandium metal complexes with monochloro-monoalkyl groups of binuclear and half-sandwich type were prepared

图6. 五苯基环戊二烯基(HCpPh5)配体稀土配合物结构

Figure 6. The structures of rare-earth complexes with pentaphenyl- cyclopentadienyl ligand

图7. (a) 四苯基环戊二烯基配体稀土配合物结构. (b) 烷基取代五苯基环戊二烯基配体稀土配合物结构

Figure 7. (a) The structures of rare-earth complexes with tetraphenylcyclopentadienyl ligand. (b) The structures of rare-earth complexes with alkyl substituted pentaphenylcyclopentadienyl ligand

图8. (a) 多芳基环戊二烯双苄基钪配合物的合成. (b) 金属镧的双三明治结构双核双氢化物的合成

Figure 8. (a) Syntheses of the aryl-substituted cyclopentadiene dibenzyl scandium complexes. (b) Synthesis of the double-sandwich bimetallic lanthanum hydride complex

图9. 双茚甲硅烷基酰胺稀土金属配合物结构

Figure 9. The structures of bisindene silylamide ligated rare-earth metal complexes

图10. (a) 碳桥连茚基稀土金属配合物结构. (b) CGC型茚基稀土金属配合物结构

Figure 10. (a) The structures of carbon-bridged indenyl ligated rare- earth metal complexes. (b) The structures of constrained geometry configuration indenyl ligated rare-earth complexes

图11. (a) 茚基双烷基钪配合物不同的攫取方式. (b) 不同路易斯碱配位的茚基双烷基稀土金属配合物结构

Figure 11. (a) Different interception methods of indenyl ligated dialkyl rare-earth metal complexes. (b) The structures of the indenyl rare-earth metals dialkyl complexes with different Lewis base ligands

图12. (a) 碳桥连芴基稀土金属配合物. (b) 硅桥连芴基稀土金属配合物

Figure 12. (a) Carbon-bridged fluorene-based ligated rare-earth metal complexes. (b) Si-bridged fluorene-based rare-earth metal complexes

图13. CGC型芴基稀土金属配合物

Figure 13. Constrained geometry configuration fluorenyl ligated rare- earth complexes

图14. 烷基取代的芴基双烷基钪配合物生成阳离子

Figure 14. Alkyl-substituted fluorenyl dialkyl scandium complexes generate cations

图15. 单核、双核半三明治结构双烷基钪配合物结构

Figure 15. The structures of mono- and binuclear half-sandwich scandium bisalkyl complexes

图16. (a) 四齿配体配位的双烷基稀土金属配合物和稀土氢化物. (b) 类CGC型四齿配体配位的双烷基稀土金属配合物结构. (c) 不同基团桥连的双苯酚稀土金属配合物结构

Figure 16. (a) Preparation of dialkyl rare-earth metal complexes and rare-earth hydrides coordinated by tetradentate ligands. (b) The structures of CGC-like tetradentate ligand coordinated dialkyl rare-earth metal complexes. (c) The structures of bisphenol rare-earth metal complexes bridged by different groups

图17. (a) 基于TpR,R'配体的稀土金属配合物结构. (b) 基于NNN型配体的稀土金属配合物结构.

Figure 17. (a) The structures of rare-earth metal complexes based with TpR,R' ligand. (b) The structures of rare-earth metal complexes based by NNN-type ligands

图18. (a) 基于ONO、CCC型三齿配体的稀土金属配合物结构. (b) 中性的三齿配体的稀土金属配合物结构

Figure 18. The structures of rare-earth metal complexes based by ONO, CCC-type tridentate ligands. (b) The structures of rare-earth metal complexes with neutral tridentate ligands

图19. 脒基配体的稀土金属配合物结构

Figure 19. The structures of rare-earth metal complexes containing amidino ligands

图20. NPN和NSN型双齿配体的稀土金属配合物结构

Figure 20. The structures of rare-earth metal complexes containing NPN and NSN-type bidentate ligands

图21. 吡啶胺基和喹啉胺基双齿配体的稀土金属配合物结构

Figure 21. The structures of rare-earth metal complexes containing pyridylamino and quinolinamino bidentate ligands

图22. β-双亚胺配体的双齿配体的稀土金属配合物结构

Figure 22. The structures of rare-earth metal complexes containing β-diketiminato bidentate ligands

图23. (a) 单齿2,6-二叔丁基苯酚配体的稀土金属配合物结构

Figure 23. (a) The structures of rare-earth metal complexes containing 2,6-di-tert-butylphenol ligand

图24. (a) 含咪唑啉-2-亚氨基配体的双烷基稀土金属配合物结构. (b) 双核芳胺基稀土金属配合物和芳胺基钪配合物结构

Figure 24. (a) The structures of dialkyl rare-earth metal complexes containing imidazoline-2-imino ligand. (b) The structures of bimetallic arylamide- ligated rare-earth metal complexes and arylamide-ligated sandium complex

参考文献 81

[1]	Wilkinson G.; Birminham J. M. J. Am. Chem. Soc. 1954, 76, 6210.
[2]	Evans W. J.; Ulibarri T. A.; Ziller J. W. J. Am. Chem. Soc. 1990, 112, 219. doi: 10.1021/ja00157a035
[3]	Evans W. J.; Gonzales S. L.; Ziller J. W. J. Am. Chem. Soc. 1991, 113, 7423. doi: 10.1021/ja00019a050
[4]	Hultzsch K. C.; Spaniol H. P.; Okuda J. Angew. Chem. Int. Ed. 1999, 38, 227. doi: 10.1002/(ISSN)1521-3773
[5]	Luo Y.; Baldamus J.; Hou Z. J. Am. Chem. Soc. 2004, 126, 13910. doi: 10.1021/ja046063p
[6]	Wang H.; Wu X.; Yang Y.; Nishiura M.; Hou Z. Angew. Chem. Int. Ed. 2020, 59, 7173. doi: 10.1002/anie.v59.18
[7]	Shapiro P. J.; Schaefer W. P.; Labimger J. A.; Bercaw J. E.; Cotter W. D. J. Am. Chem. Soc. 1994, 116, 4623. doi: 10.1021/ja00090a011
[8]	Arndt S.; Okuda J. Chem. Rev. 2002, 102, 1953. doi: 10.1021/cr010313s
[9]	Zhang L.; Luo Y.; Hou Z. J. Am. Chem. Soc. 2005, 127, 14562. doi: 10.1021/ja055397r
[10]	Huang L.; Liu Z.; Zhang Y.; Wu C.; Cui D. ACS Catal. 2022, 12, 953. doi: 10.1021/acscatal.1c04976
[11]	Chen R.; Yao C.; Wang M.; Xie H.; Wu C.; Cui D. Organometallics 2015, 34, 455. doi: 10.1021/om500992v
[12]	Liu Z.; Liu B.; Zhao Z.; Cui D. Macromolecules 2021, 54, 3181. doi: 10.1021/acs.macromol.1c00009
[13]	Wang T.; Wu C.; Cui D. Macromolecules 2020, 53, 6380. doi: 10.1021/acs.macromol.0c01160
[14]	Peng D.; Du G.; Zhang P.; Yao B.; Li X.; Zhang S. Macromol. Rapid Commun. 2016, 37, 987. doi: 10.1002/marc.v37.12
[15]	Chen J.; Gao Y.; Wang B.; Lohr T. L.; Marks T. J. Angew. Chem. Int. Ed. 2017, 56, 15964. doi: 10.1002/anie.v56.50
[16]	Desurmont G.; Tanaka M.; Li Y.; Yasuda H.; Tokimitsu T.; Tone S.; Yanagase A. J. Polym. Sci. Pol. Chem. 2000, 38, 4095. doi: 10.1002/(ISSN)1099-0518
[17]	Wang Y.; Zhou C.; Cheng J. Macromolecules 2020, 53, 3332. doi: 10.1021/acs.macromol.9b02602
[18]	Forsyth C. M.; Deacon G. B.; Field L. D.; Jones C.; Junk P. C.; Kay D. L.; Masters A. F.; Richards A. F. Chem. Commun. 2006, 9, 1003.
[19]	Kelly R. P.; Bell T. D. M.; Cox R. P.; Daniels D. P.; Deacon G. B.; Jaroschik F.; Junk P. C.; Le Goff X. F.; Lemercier G.; Martinez A.; Wang J.; Werner D. Organometallics 2015, 34, 5624. doi: 10.1021/acs.organomet.5b00842
[20]	Deacon G. B.; Jaroschik F.; Junk P. C.; Kelly R. P. Chem. Commun. 2014, 50, 10655. doi: 10.1039/C4CC04427D
[21]	Ruspic C.; Moss J. R.; Schuermann M.; Harder S. Angew. Chem. Int. Ed. 2008, 47, 2121. doi: 10.1002/(ISSN)1521-3773
[22]	Wang Y.; Cheng J. New J. Chem. 2020, 44, 17333. doi: 10.1039/D0NJ03852K
[23]	Wang Y.; Rosal I. D.; Qin G.; Zhao L.; Maron L.; Shi X.; Cheng J. Chem. Commun. 2021, 57, 7766. doi: 10.1039/D1CC01841H
[24]	Tardif O.; Kaita S. Dalton Trans. 2008, 19, 2531.
[25]	Rodrigues A.; Kirillov E.; Roisnel T.; Razavi A.; Vuillemin B.; Carpentier J. Angew. Chem. Int. Ed. 2007, 46, 7240. doi: 10.1002/(ISSN)1521-3773
[26]	Jiang Y.; Zhang Z.; Li S.; Cui D. Angew. Chem. Int. Ed. 2022, 61, e202112966.
[27]	Wang B.; Wang D.; Cui D.; Gao W.; Tang T.; Chen X.; Jing X. Organometallics 2007, 26, 3167. doi: 10.1021/om0700922
[28]	Pan Y.; Rong W.; Jian Z.; Cui D. Macromolecules 2012, 45, 1248. doi: 10.1021/ma202558g
[29]	Xu X.; Chen Y.; Sun J. Chem. Eur. J. 2009, 15, 846. doi: 10.1002/chem.200802220
[30]	Xu X.; Chen Y.; Feng J.; Zou G.; Sun J. Organometallics 2010, 29, 549. doi: 10.1021/om900758y
[31]	Tan R.; Mu X.; Wang H.; Li Y. Polymer 2021, 230, 124085. doi: 10.1016/j.polymer.2021.124085
[32]	Kirillov E.; Lehmann C. W.; Razavi A.; Carpentier J. J. Am. Chem. Soc. 2004, 126, 12240. pmid: 15453737
[33]	Rodrigues A.; Kirillov E.; Lehmann C. W.; Roisnel T.; Vuillemin B.; Razavi A.; Carpentier J. Chem. Eur. J. 2007, 13, 5548. doi: 10.1002/(ISSN)1521-3765
[34]	Rodrigues A.; Kirillov E.; Vuillemin B.; Razavi A.; Carpentier J. Polymer 2008, 49, 2039. doi: 10.1016/j.polymer.2008.02.043
[35]	Thuilliez J.; Monteil V.; Spitz R.; Boisson C. Angew. Chem. Int. Ed. 2005, 44, 2593. doi: 10.1002/(ISSN)1521-3773
[36]	Thuilliez J.; Spitz R.; Boisson C. Macromol. Chem. Phys. 2006, 207, 1727. doi: 10.1002/(ISSN)1521-3935
[37]	Thuilliez J.; Ricard L.; Nief F.; Boisson F.; Boisson C. Macromolecules 2009, 42, 3774. doi: 10.1021/ma9003852
[38]	Li S.; Liu D.; Wang Z.; Cui D. ACS Catal. 2018, 8, 6086. doi: 10.1021/acscatal.8b00885
[39]	Lin F.; Wang X.; Pan Y.; Wang M.; Liu B.; Luo Y.; Cui D. ACS Catal. 2015, 6, 176. doi: 10.1021/acscatal.5b02334
[40]	Liu B.; Qiao K.; Fang J.; Wang T.; Wang Z.; Liu D.; Xie Z.; Maron L.; Cui D. Angew. Chem. Int. Ed. 2018, 57, 14896. doi: 10.1002/anie.201808836 pmid: 30232826
[41]	Zhong Y.; Wu Y.; Cui D. Macromolecules 2021, 54, 1754. doi: 10.1021/acs.macromol.0c02777
[42]	Li X.; Wang X.; Tong X.; Zhang H.; Chen Y.; Liu Y.; Liu H.; Wang X.; Nishiura M.; He H.; Lin Z. G.; Zhang S. W.; Hou Z. Organometallics 2013, 32, 1445. doi: 10.1021/om3011036
[43]	Zhang Z.; Kang X.; Jiang Y.; Cai Z.; Li S.; Cui D. Angew. Chem. Int. Ed. 2023, e202215582.
[44]	Ohashi M.; Konkol M.; Del Rosal I.; Poteau R.; Maron L.; Okuda J. J. Am. Chem. Soc. 2008, 130, 6920. doi: 10.1021/ja801771u
[45]	Bambirra S.; van Leusen D.; Meetsma A.; Hessen B.; Teuben J. H. Chem. Commun. 2001, 7, 637.
[46]	Bambirra S.; Meetsma A.; Hessen B.; Bruins A. P. Organometallics 2006, 25, 3486. doi: 10.1021/om060278l
[47]	Bambirra S.; van Leusen D.; Tazelaar C. G. J.; Meetsma A.; Hessen B. Organometallics 2007, 26, 1014. doi: 10.1021/om060870a
[48]	Tazelaar C. G. J.; Bambirra S.; van Leusen D.; Meetsma A.; Hessen B.; Teuben J. H. Organometallics 2004, 23, 936. doi: 10.1021/om034403u
[49]	Ma H. Y.; Spaniol T. P.; Okuda J. Dalton Trans. 2003, 24, 4770.
[50]	Long D. P.; Bianconi P. A. J. Am. Chem. Soc. 1996, 118, 12453. doi: 10.1021/ja962169b
[51]	Yi W.; Zhang J.; Zhang F.; Zhang Y.; Chen Z.; Zhou X. Chem. Eur. J. 2013, 19, 11975. doi: 10.1002/chem.201300610
[52]	Cheng J.; Saliu K.; Kiel G. Y.; Ferguson M. J.; McDonald R.; Takats J. Angew. Chem. Int. Ed. 2008, 47, 4910. doi: 10.1002/(ISSN)1521-3773
[53]	Estler F.; Eickerling G.; Herdtweck E.; Anwander R. Organometallics 2003, 22, 1212. doi: 10.1021/om020783s
[54]	Zimmermann M.; Törnroos K. W.; Waymouth R. M.; Anwander R. Organometallics 2008, 27, 4310. doi: 10.1021/om701195x
[55]	Zhang L.; Suzuki T.; Luo Y.; Nishiura M.; Hou Z. Angew. Chem. Int. Ed. 2007, 119, 1941. doi: 10.1002/(ISSN)1521-3757
[56]	Chen H.-X.; Li B.-X.; Yao Y.-M.; Liu P. Chin. J. Appl. Chem. 2022, 39, 843. (in Chinese)
	(陈洪霞, 李宝霞, 姚英明, 刘朋, 应用化学, 2022, 39, 843.) doi: 10.19894/j.issn.1000-0518.210482
[57]	Lv K.; Cui D. Organometallics 2008, 27, 5438. doi: 10.1021/om800801k
[58]	Hajela S.; Schaefer W. P.; Bercaw J. E. J. Organomet. Chem. 1997, 532, 45. doi: 10.1016/S0022-328X(96)06768-X
[59]	Lawrence S. C.; Ward B. D.; Dubberley S. R.; Kozak C. M.; Mountford P. Chem. Commun. 2003, 23, 2880.
[60]	Tredget C. S.; Bonnet F.; Cowley A. R.; Mountford P. Chem. Commun. 2005, 26, 3301.
[61]	Wedler M.; Noltemeyer M.; Pieper U.; Schmidt H. G.; Stalke D.; Edelmann F. T. Angew. Chem. Int. Ed. 1990, 29, 894. doi: 10.1002/(ISSN)1521-3773
[62]	Welder M.; Recknagel A.; Gilje J. W.; Nottemeyer M.; Edelmann F. T. J. Organomet. Chem. 1992, 426, 295. doi: 10.1016/0022-328X(92)83063-N
[63]	Bambirra S.; Brandsma M.; Brussee E.; Meetsma A.; Hessen B.; Teuben J. H. Organometallics 2000, 19, 3197. doi: 10.1021/om0001063
[64]	Bambirra S.; van Leusen D.; Meetsma A.; Hessen B.; Teuben J. H. Chem. Commun. 2003, 4, 522.
[65]	Bambirra S.; Bouwkamp M. W.; Meetsma A.; Hessen B. J. Am. Chem. Soc. 2004, 126, 9182. pmid: 15281798
[66]	Zhang L.; Nishiura M.; Yuki M.; Luo Y.; Hou Z. Angew. Chem. Int. Ed. 2008, 47, 2642. doi: 10.1002/(ISSN)1521-3773
[67]	Li S.; Miao W.; Tang T.; Dong W.; Zhang X.; Cui D. Organometallics 2008, 27, 718. doi: 10.1021/om700945r
[68]	Li S.; Cui D.; Li D.; Hou Z. Organometallics 2009, 28, 4814. doi: 10.1021/om900261n
[69]	Liu B.; Li L.; Sun G.; Liu J.; Wang M.; Li S.; Cui D. Macromolecules 2014, 47, 4971. doi: 10.1021/ma501085c
[70]	Spannenberg A.; Arndt P.; Kempe R. Angew. Chem. Int. Ed. 1998, 37, 832. doi: 10.1002/(SICI)1521-3773(19980403)37:6【-逻辑与-】lt;832::AID-ANIE832【-逻辑与-】gt;3.0.CO;2-A pmid: 29711387
[71]	Qayyum S.; Haberland K.; Forsyth C. M.; Junk P. C.; Deacon G. B.; Kempe R. Eur. J. Inorg. Chem. 2008, 2008, 557. doi: 10.1002/ejic.v2008:4
[72]	Lee L. W. M.; Piers W. E.; Elsegood M. R. J.; Clegg W.; Parvez M. Organometallics 1999, 18, 2947. doi: 10.1021/om9903801
[73]	Hayes P. G.; Piers W. E.; Parvez M. J. Am. Chem. Soc. 2003, 125, 5622. pmid: 12733887
[74]	Hayes P. G.; Piers W. E.; McDonald R. J. Am. Chem. Soc. 2002, 124, 2132. pmid: 11878964
[75]	Hayes P. G.; Piers W. E.; Lee L. W. M.; Knight L. K.; Parvez M.; Elsegood M. R. J.; Clegg W. Organometallics 2001, 20, 2533. doi: 10.1021/om010131o
[76]	Li D.; Li S.; Cui D.; Zhang X. Organometallics 2010, 29, 2186. doi: 10.1021/om100100r
[77]	Huang J.; Yao C.; Li S.; Cui D. Chinese J. Polym. Sci. 2021, 39, 309. doi: 10.1007/s10118-021-2505-3
[78]	Evans W. J.; Broomhall D. R.; Ziller J. W. Organometallics 1996, 15, 1351. doi: 10.1021/om9508400
[79]	Butovskii M. V.; Tok O. L.; Bezugly V.; Wagner F. R.; Kempe R. Angew. Chem. Int. Ed. 2011, 50, 7695. doi: 10.1002/anie.201102363 pmid: 21717547
[80]	Luo Y.; Nishiura M.; Hou Z. J. Organomet. Chem. 2007, 692, 536. doi: 10.1016/j.jorganchem.2006.06.048
[81]	Wang C.; Chen J.; Xu W.; Mou Z.; Yao Y.; Luo Y. Inorg. Chem. 2020, 59, 3132. doi: 10.1021/acs.inorgchem.9b03495