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Updated: Aug 26, 2025

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes
Published on: February 27, 2017
Non-π-Allyl Mechanism for the 1,4-cis-Butadiene Polymerization: Theoretical Study of Polymerization via Insertion of
Rika Fukushima1, Olivier Tardif1, Shojiro Kaita1
1Advanced Materials Division, Bridgestone Corporation, 187-8531, Kodaira-shi, Tokyo, Japan.
Abstract:
This paper reports a computational study on the specific 1,4-cis polymerization of butadiene catalyzed by the cationic gadolinium metallocene [(C5 Me5 )2 Gd][B(C6 F5 )4 ] combined with excess amount of Al(i Bu)3 . Because this reaction system has no initial Gd-alkyl bond, a mechanism with conventional coordinative chain transfer polymerization (CCTP) is not feasible. Density functional theory (DFT) analyses indicate a novel mechanism in which the cationic Gd plays a crucial role by assisting butadiene insertion into one of the Al-C bond of Al(i Bu)3 . The proposed butadiene polymerization mechanism can account for the specific 1,4-cis selectivity of this catalyst system.
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