Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization

Biao Li; Yuan-Bo Liu; Ying-Li Ding; Li Pan; Yue-Sheng Li

doi:10.1007/s10118-025-3443-2

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Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization

RESEARCH ARTICLE | Updated：2025-12-03

- Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization
- Chinese Journal of Polymer Science Vol. 43, Issue 12, Pages: 2299-2309(2025)
- Affiliations：
  
  a.School of Materials Science and Engineering, State Key Laboratory of High-Performance Roll Materials and Composite Forming, Tianjin University, Tianjin 300350, China
  b.PetroChina Refining, Chemicals & New Materials Company, Beijing 100007, China
  c.Tianjin Key Laboratory of Composite and Functional Materials, Key Laboratory of Organic Integrated Circuits, Ministry of Education, Tianjin 300350, China
- Author bio：
  
  lilypan@tju.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3443-2
  CLC：
- Received：24 July 2025，
  
  Accepted：22 August 2025，
  
  Published Online：12 November 2025，
  
  Published：15 December 2025
- Accepted：
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Li, B.; Liu, Y. B.; Ding, Y. L.; Pan, L.; Li, Y. S. Super-high active, homogeneous vanadium(V) complexes bearing bidentate phenoxy-phosphine ligands for diverse olefins (co)polymerization. Chinese J. Polym. Sci. 2025, 43, 2299–2309

Biao Li, Yuan-Bo Liu, Ying-Li Ding, et al. Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2299-2309.
Li, B.; Liu, Y. B.; Ding, Y. L.; Pan, L.; Li, Y. S. Super-high active, homogeneous vanadium(V) complexes bearing bidentate phenoxy-phosphine ligands for diverse olefins (co)polymerization. Chinese J. Polym. Sci. 2025, 43, 2299–2309 DOI： 10.1007/s10118-025-3443-2.

Biao Li, Yuan-Bo Liu, Ying-Li Ding, et al. Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2299-2309. DOI： 10.1007/s10118-025-3443-2.

摘要

Vanadium complexes bearing bidentate phenoxy-phosphine ligands demonstrated remarkable efficiency in ethylene homopolymerization and copolymerization with various olefins. Their catalytic performance was strongly influenced by the electronic and steric environment of ligands and comonomers. These results highlight the importance of rational ligand design and comonomer selection in optimizing catalyst performance.

Abstract

A series of imido-vanadium(V) complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR

elemental analysis

and single-crystal X-ray diffraction. These complexes demonstrated excellent catalytic performance in ethylene/1-hexene copolymerization

achieving high activities of 12.0×10

–49.0×10

polymer

·(mol

)

–1

·h

–1

and affording random copolymers with tunable 1-hexene incorporations. These catalysts also exhibited ultrahigh activity

to 112.2×10

polymer

·(mol

)

–1

·h

–1

in ethylene/norbornene (NB) copolymerization

yielding cyclic olefin copolymers with adjustable NB incorporations. Remarkably

these catalysts demonstrated exceptional tolerance toward polar functional groups

enabling efficient copolymerization of ethylene with both 10-undecen-1-ol (U-OH) and 5-norbornene-2-methanol (NB-OH)

incorporating about 2 mol% polar comonomers with high efficiency. Different with the catalytic behaviors in copolymerization of ethylene with nonpolar comonomers

the catalytic activities in E/U-OH copolymerization (25.7×10

polymer

·(mol

)

–1

·h

–1

) were much higher than those in E/NB-OH copolymerization (8.6×10

polymer

·(mol

)

–1

·h

–1

). DFT calculations revealed that the catalytic performance is governed by synergistic electronic and steric effects. For E/NB copolymerization

strong preference for cyclic olefins was attributed to favorable transition state stabilization. In polar comonomer systems

steric effects were predominant

with NB-OH exhibiting a larger buried volume around vanadium center upon coordination compared to U-OH. Overall

this work provides fundamental insights into vanadium-catalyzed (co)polymerization and offers new strategies for tailored polyolefin design.

关键词

Keywords

references

Nomura, K.; Tsubota, M.; Fujiki, M. Efficient ethylene/norbornene copolymerization by (aryloxo)(indenyl)titanium(IV) complexes−MAO catalyst system. Macromolecules 2003 , 36 , 3797−3799..

Wolff, F.; Lorber, C.; Choukroun, R.; Donnadieu, B. Vanadium(V) complexes of a chelating dianionic [ONNO ] -type amine bis(phenolate) ligand: synthesis and solid state and solution structures. Inorg. Chem. 2003 , 42 , 7839−7845..

Zhang, Y.; Mu, Y.; Lü, C.; Li, G.; Xu, J.; Zhang, Y.; Zhu, D.; Feng, S. Constrained geometry tetramethylcyclopentadienyl-phenoxy titanium dichlorides: template synthesis, structures, and catalytic properties for ethylene polymerization. Organometallics 2004 , 23 , 540−546..

He, L.; Liu, J.; Li, Y.; Liu, S.; Li, Y. High-temperature living copolymerization of ethylene with norbornene by titanium complexes bearing bidentate [O, P ] ligands. Macromolecules 2009 , 42 , 8566−8570..

[Lorber, C. [ONNO ] -type amine bis(phenolate)-based vanadium catalysts for ethylene homo- and copolymerization. Pure Appl. Chem . 2009 , 81 , 1205-1215..

Zhang, S.; Nomura, K. Highly efficient dimerization of ethylene by (imido)vanadium complexes containing (2-anilidomethyl)pyridine ligands: notable ligand effect toward activity and selectivity. J. Am. Chem. Soc. 2010 , 132 , 4960−4965..

Tao, X.; Wu, Q.; Huo, H.; Gao, W.; Mu, Y. New titanium(IV) complexes with 2-cyclopentadienylbenzylamido ligands: synthesis, characterization, and catalytic properties for ethylene polymerization and co polymerization with 1-hexene. Organometallics 2013 , 32 , 4185−4191..

Vaccarello, D. N.; O’Connor, K. S.; Iacono, P.; Rose, J. M.; Cherian, A. E.; Coates, G. W. Synthesis of semicrystalline polyolefin materials: precision methyl branching via stereoretentive chain walking. J. Am. Chem. Soc. 2018 , 140 , 6208−6211..

Zanchin, G.; Vendier, L.; Pierro, I.; Bertini, F.; Ricci, G.; Lorber, C.; Leone, G. Homo- and co-polymerization of ethylene with cyclic olefins catalyzed by phosphine adducts of (imido)vanadium(IV) complexes. Organometallics 2018 , 37 , 3181−3195..

Wang, X.; Zhang, Y.; Wang, F.; Pan, L.; Wang, B.; Li, Y. Robust and reactive neutral nickel catalysts for ethylene polymerization and copolymerization with a challenging 1,1-disubstituted difunctional polar monomer. ACS Catal. 2021 , 11 , 2902−2911..

Feng, W.; Liu, C.; Liu, S.; Li, Z. Hafnium and zirconium complexes bearing ONN-tridentate ligands and their catalytic properties toward olefin polymerization. Organometallics 2023 , 42 , 3466−3473..

Wu, R.; Niu, Z.; Xia, Z.; He, J.; Bai, C. Vanadium complexes bearing 8-anilide-5,6,7-trihydroquinoline ligands for ethylene (co-) polymerization. Dalton Trans. 2023 , 52 , 8636−8644..

Diteepeng, N.; Tang, X.; Hou, X.; Li, Y.; Phomphrai, K.; Nomura, K. Ethylene polymerisation and ethylene/norbornene copolymerisation by using aryloxo-modified vanadium(V) complexes containing 2,6-difluoro-, dichloro-phenylimido complexes. Dalton Trans. 2015 , 44 , 12273−12281..

Soshnikov, I. E.; Semikolenova, N. V.; Bryliakov, K. P.; Zakharov, V. A.; Redshaw, C.; Talsi, E. P. An EPR study of the vanadium species formed upon interaction of vanadyl N and C-capped tris(phenolate) complexes with AlEt 3 and AlEt 2 Cl. J. Mol. Catal. A: Chem. 2009 , 303 , 23−29..

Soshnikov, I. E.; Semikolenova, N. V.; Shubin, A. A.; Bryliakov, K. P.; Zakharov, V. A.; Redshaw, C.; Talsi, E. P. EPR monitoringof vanadium(IV) species formed upon activation of vanadium(V) polyphenolate precatalysts with AlR 2 Cl and AlR 2 Cl/ethyltrichloroacetate (R=Me, Et). Organometallics 2009 , 28 , 6714−6720..

Zhang, S.; Zhang, W.; Shang, D.; Zhang, Z.; Wu, Y. Ethylene /propylene copolymerization catalyzed by vanadium complexes containing N-heterocyclic carbenes. Dalton Trans. 2015 , 44 , 15264−15270..

Zhang, S.; Zhang, W.; Shang, D.; Wu, Y. Synthesis of ultra-high-molecular-weight ethylene-propylene copolymer via quasi-living copolymerization with N-heterocyclic carbene ligated vanadium complexes. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57 , 553−561..

Wang, Y.; Zha, H.; Cheng, P.; Zhang, S.; Liu, X.; Wu, Y. Vanadium(V) complexes containing unsymmetrical N-heterocyclic carbene ligands: highly efficient synthesis and catalytic behavior towards ethylene/propylene copolymerization. Chinese J. Polym. Sci. 2024 , 42 , 32−41..

Leone, G.; Zanchin, G.; Di Girolamo, R.; De Stefano, F.; Lorber, C.; De Rosa, C.; Ricci, G.; Bertini, F. Semibatch terpolymerization of ethylene, propylene, and 5-ethylidene-2-norbornene: heterogeneous high-ethylene EPDM thermoplastic elastomers. Macromolecules 2020 , 53 , 5881−5894..

Wang, M.; Li, T.; Guo, Y.; Bai, C.; Qi, Y.; Liu, L. Synthesis of liquid EPDM having ultra-low-viscosity for curing at room temperature. Polymer 2024 , 303 , 127138..

Soshnikov, I. E.; Semikolenova, N. V.; Bryliakov, K. P.; Shubin, A. A.; Zakharov, V. A.; Redshaw, C.; Talsi, E. P. An EPR study of the V(IV) species formed upon activation of a vanadyl phenoxyimine polymerization catalyst with AlR 3 and AlR 2 Cl (R=Me, Et). Macromol. Chem. Phys. 2009 , 210 , 542−548..

Nomura, K.; Oshima, M.; Mitsudome, T.; Harakawa, H.; Hao, P.; Tsutsumi, K.; Nagai, G.; Ina, T.; Takaya, H.; Sun, W.; Yamazoe, S. Synthesis and structural analysis of (imido)vanadium dichloride complexes containing 2-(2′-benz-imidazolyl)pyridine ligands: effect of Al cocatalyst for efficient ethylene (co)polymerization. ACS Omega 2017 , 2 , 8660−8673..

Zhang, X.; Li, H.; Xiang, B.; Liu, X.; Zhang, S.; Wu, Y. Imidazolidin-2-iminato vanadium complexes for the synthesis of ethylene/propylene/5-ethylidene-2-norbornene (ENB) terpolymers with high ENB incorporation and ultra-high molecular weight. Polym. Chem. 2024 , 15 , 2148−2156..

Li, Z.; Yin, C.; Zhang, J.; Zhang, T.; Gao, X.; Hou, X. Synthesis of vanadium(V) complex with bulky phenoxy ligand and the study of catalysis behavior in ethylene (co)polymerization. Polymer 2024 , 293 , 126680..

Wu, J.; Mu, J.; Zhang, S.; Li, Y. Vanadium(V) complexes containing tetradentate amine trihydroxy ligands as catalysts for copolymerization of cyclic olefins. J. Polym. Sci., Part A: Polym. Chem. 2010 , 48 , 1122−1132..

Li, Y.; Yang, J.; Wang, B.; Li, Y. Efficient copolymerization of ethylene with norbornene or its derivatives using half-metallocene zirconium(Ⅳ) catalysts. RSC Adv. 2016 , 6 , 59590−59599..

Li, J.; Liu, Y.; Mu, H.; Jian, Z. Mono- and bi-nuclear phosphine-phenolate neutral nickel catalysts via simple Schiff-base condensation for ethylene polymerization. J. Catal. 2024 , 432 , 115413..

De Stefano, F.; Baur, M.; De Rosa, C.; Mecking, S. Keto-polyethylenes with controlled crystallinity and materials properties from catalytic ethylene- co -norbornene terpolymerization. Macromolecules 2024 , 57 , 1072−1079..

Xiong, S.; Hong, A.; Ghana, P.; Bailey, B. C.; Spinney, H. A.; Bailey, H.; Henderson, B. S.; Marshall, S.; Agapie, T. Acrylate-induced β -H elimination in coordination insertion copolymerizaton catalyzed by nickel. J. Am. Chem. Soc. 2023 , 145 , 26463−26471..

Wang, W.; Nie, N.; Xu, M.; Zou, C. Lewis acid modulation in phosphorus phenol nickel catalyzed ethylene polymerization and copolymerization. Polym. Chem. 2023 , 14 , 4933−4939..

Xie, Y.; Yang, F.; Miao, Q.; Zhang, Z.; Wang, W.; Wang, F.; Zou, C. Electronic effect regulated ethylene polymerization and copolymerization of phosphorus phenol nickel catalysts. Appl. Organomet. Chem. 2024 , 38 , e7469..

Peng, D.; He, H.; Pang, W.; Behzadi, S.; Qasim, M. Synthesis of UHMWPE by neutral phosphine-phenolate based nickel catalysts. Polymer 2023 , 280 , 126019..

Liu, Y.; Wang, C.; Mu, H.; Jian, Z. Aqueous coordination-insertion copolymerization for producing high molecular weight polar polyolefins. Angew. Chem. Int. Ed. 2024 , 63 , e202404392..

Zhang, Y.; Mu, H.; Pan, L.; Wang, X.; Li, Y. Robust bulky [P, O ] neutral nickel catalysts for copolymerization of ethylene with polar vinyl monomers. ACS Catal. 2018 , 8 , 5963−5976..

Zhang, S.; Lu, L.; Li, B.; Li, Y. Synthesis, structural characterization, and olefin polymerization behavior of vanadium(III) complexes bearing bidentate phenoxy-phosphine ligands. J. Polym. Sci., Part A: Polym. Chem. 2012 , 50 , 4721−4731..

Goryunov, G. P.; Sharikov, M. I.; Iashin, A. N.; Canich, J. A. M.; Mattler, S. J.; Hagadorn, J. R.; Uborsky, D. V.; Voskoboynikov, A. Z. Rigid postmetallocene catalysts for propylene polymerization: ligand design prevents the temperature-dependent loss of stereo- and regioselectivities. ACS Catal. 2021 , 11 , 8079−8086..

Li, F.; He, J.; Song, T.; Gao, W.; Mu, X.; Mu, Y. Zirconium complexes with bulkier amine bis(phenolate) ligands and their catalytic properties for ethylene (co)polymerization. Inorg. Chem. 2022 , 61 , 6469−6479..

Li, F.; Bai, Y.; He, J.; Song, T.; Gao, W.; Mu, X.; Mu, Y. Synthesis of ultrahigh molecular weight ethylene-based (co)polymers with titanium complexes bearing nonsymmetric amine-bis(phenolate) ligands. Macromolecules 2023 , 56 , 6764−6775..

Buijink, J. F.; Teuben, J. H.; Kooijman, H.; Spek, A. L. Synthesis, molecular structure, and reactivity of a half-sandwich vanadium(III) imido complex: the first vanadium(V) alkylidene. Organometallics 1994 , 13 , 2922−2924..

[Lu, L.; Wang, J.; Liu, J.; Li, Y. Synthesis, structural characterization, and ethylene polymerization behavior of (arylimido)vanadium(V) complexes bearing tridentate Schiff base ligands. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 , 2633-2642..

[Hao, Z.; Li, F.; Gao, W. o -Trityl phenoxy-imino vanadium(III) complexes: synthesis, characterization, and catalysis on ethylene (co)polymerization. Appl. Organomet. Chem . 2020 , 34 , e5809..

Tang, X.; Wang, Y.; Li, B.; Liu, J.; Li, Y. Highly efficient ethylene/norbornene copolymerization by o -di(phenyl)phosphanyl- phenolate-based half-titanocene complexes. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51 , 1585−1594..

Falivene, L.; Credendino, R.; Poater, A.; Petta, A.; Serra, L.; Oliva, R.; Scarano, V.; Cavallo, L. SambVca 2. A web tool for analyzing catalytic pockets with topographic steric m aps. Organometallics 2016 , 35 , 2286−2293..

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