Ring Opening Polymerization of <italic style="font-style: italic">ω</italic>-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky <italic style="font-style: italic">α</italic>-Diimine Ligands

Li-Jia Liu; Wen-Peng Zhao; Li-Shuang Ma; Chun-Yu Zhang; Feng Wang; Xue-Quan Zhang; Heng Liu

doi:10.1007/s10118-025-3303-0

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Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands

RESEARCH ARTICLE | Updated：2025-07-14

- Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands
- Chinese Journal of Polymer Science Vol. 43, Issue 4, Pages: 640-654(2025)
- Affiliations：
  
  a.Shandong Provincial College Laboratory of Rubber Material and Engineering/Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
  b.College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
- Author bio：
  
  zwp@qust.edu.cn (W.P.Z.)
  fengwang@qust.edu.cn (F.W.)
  hengliu@qust.edu.cn (H.L.)
- Funds：
- DOI：10.1007/s10118-025-3303-0
  CLC：
- Received：31 October 2024，
  
  Revised：2024-12-23，
  
  Accepted：29 December 2024，
  
  Online First：13 March 2025，
  
  Published：01 April 2025
- Accepted：
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Liu, L. J.; Zhao, W. P.; Ma, L. S.; Zhang, C. Y.; Wang, F.; Zhang, X. Q.; Liu, H. Ring opening polymerization of ω-pentadecalactone by weakly oxophilic Fe(II)-based catalytic systems bearing bulky α-diimine ligands. Chinese J. Polym. Sci. 2025, 43, 640–654

Li-Jia Liu, Wen-Peng Zhao, Li-Shuang Ma, et al. Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands[J]. Chinese Journal of Polymer Science, 2025, 43(4): 640-654. DOI: 10.1007/s10118-025-3303-0.
Liu, L. J.; Zhao, W. P.; Ma, L. S.; Zhang, C. Y.; Wang, F.; Zhang, X. Q.; Liu, H. Ring opening polymerization of ω-pentadecalactone by weakly oxophilic Fe(II)-based catalytic systems bearing bulky α-diimine ligands. Chinese J. Polym. Sci. 2025, 43, 640–654 DOI： 10.1007/s10118-025-3303-0.

Li-Jia Liu, Wen-Peng Zhao, Li-Shuang Ma, et al. Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands[J]. Chinese Journal of Polymer Science, 2025, 43(4): 640-654. DOI: 10.1007/s10118-025-3303-0. DOI：

摘要

A family of bulky

-diimine Fe(II) complexes were reported to catalyze ring opening polymerization (ROP) of a large ring-sized macrolactone

-pentadecalactone (PDL)

with high catalytic efficiencies. With the aid of bulky nature of the ligands

transesterification reactions could be significantly suppressed

allowing the polymerization proceed in a living-like manner.

Abstract

High catalytic efficiencies in ring opening polymerization (ROP) of a large ring-sized macrolactone

-pentadecalactone (PDL)

by using transition metal Fe(II)-based catalysts were achieved for the first time in this study. Benefited from the bulky nature of the ligated

-diimine ligands

as evidenced from single-crystal structures

as well as the weakly oxophilic nature of the metal centers

chain transesterification reactions could be partially suppressed

allowing the polymerization proceed in a living-like and semi-controllable manner

i.e.

good linear dependence of propagation rates on catalyst concentration and PDL concentration as observed in the detailed kinetics studies. The whole polymerization proceeds

via

a “coordination-insertion” mechanism

and with the aid of density functional theory (DFT) calculation studies

a “slow insertion → fast elimination” manner was demonstrated for the monomer propagation step

suggesting the insertion of Fe-OR into the carbonyl group C＝O as the rate-determining step. The present catalytic system also showed fast chain transfer reactions to alcohol compounds

affording quasi-immortal characteristics. DFT calculations showed that such a transfer reaction only required an energy barrier of 6.4 kcal/mol

performing a good consistency with the fast

chain transfer rates.

关键词

Keywords

references

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Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands

DOI：10.1007/s10118-025-3303-0

摘要

Abstract

关键词

Keywords

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