Stereoselective trans -1,4 Polymerization of Isoprene and β -Myrcene Mediated by Iron Complexes Bearing 1,1-Diaryl- N -(quinolin-8-yl)methanimine Ligands
Abstract
Although iron has emerged as an earth-abundant alternative for 1,3-diene coordinative polymerization, stereoselective iron systems remain uncommon and are often associated with limited catalytic activity. Here, we report three iron(II) complexes supported by 1,1-diaryl-N-(quinolin-8-yl)methanimine ligands, which upon activation with Al(iBu)3/[CPh3][B(C6F5)4] or methylaluminoxane (MAO), promote trans-1,4-selective polymerization of isoprene and β-myrcene with high activity (TOF up to 5700 h–1 at room temperature) and trans-1,4 contents of up to 95 and 99%, respectively. These systems operate under mild conditions and afford polymers with tunable molar masses by varying the monomer-to-Fe ratio. Beyond homopolymers, the catalyst platform allows the synthesis of poly(isoprene-block-myrcene) through sequential copolymerization, yielding trans-1,4-stereoregular materials. Density functional theory (DFT) calculations provide mechanistic insights into the origin of the trans-1,4 selectivity, rationalizing the experimentally observed selectivity. This work demonstrates that well-defined iron catalysts can efficiently mediate trans-selective 1,3-diene polymerization with high activity, highlighting the potential of iron for the development of precision polymerization catalysts.
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BibTeX
@article{caulier2026stereoselective,
title = {{Stereoselective trans -1,4 Polymerization of Isoprene and β -Myrcene Mediated by Iron Complexes Bearing 1,1-Diaryl- N -(quinolin-8-yl)methanimine Ligands}},
author = {Raphael Caulier and Subash Arjunan and Frederic Capet and Marc Bria and Iker del Rosal and Chiara Dinoi and Marc Visseaux and Yohan Champouret},
journal = {ACS Catalysis},
year = {2026},
month = sep,
doi = {10.1021/acscatal.6c04103},
url = {https://hal.science/hal-05739484v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Stereoselective trans -1,4 Polymerization of Isoprene and β -Myrcene Mediated by Iron Complexes Bearing 1,1-Diaryl- N -(quinolin-8-yl)methanimine Ligands
AU - Raphael Caulier
AU - Subash Arjunan
AU - Frederic Capet
AU - Marc Bria
AU - Iker del Rosal
AU - Chiara Dinoi
AU - Marc Visseaux
AU - Yohan Champouret
PY - 2026
DA - 2026/09/04
JO - ACS Catalysis
DO - 10.1021/acscatal.6c04103
UR - https://hal.science/hal-05739484v1
AB - Although iron has emerged as an earth-abundant alternative for 1,3-diene coordinative polymerization, stereoselective iron systems remain uncommon and are often associated with limited catalytic activity. Here, we report three iron(II) complexes supported by 1,1-diaryl-N-(quinolin-8-yl)methanimine ligands, which upon activation with Al(iBu)3/[CPh3][B(C6F5)4] or methylaluminoxane (MAO), promote trans-1,4-selective polymerization of isoprene and β-myrcene with high activity (TOF up to 5700 h–1 at room temperature) and trans-1,4 contents of up to 95 and 99%, respectively. These systems operate under mild conditions and afford polymers with tunable molar masses by varying the monomer-to-Fe ratio. Beyond homopolymers, the catalyst platform allows the synthesis of poly(isoprene-block-myrcene) through sequential copolymerization, yielding trans-1,4-stereoregular materials. Density functional theory (DFT) calculations provide mechanistic insights into the origin of the trans-1,4 selectivity, rationalizing the experimentally observed selectivity. This work demonstrates that well-defined iron catalysts can efficiently mediate trans-selective 1,3-diene polymerization with high activity, highlighting the potential of iron for the development of precision polymerization catalysts.
SN - 2155-5435
SN - 2155-5435
ER -