Front Cover: Non‐π‐Allyl Mechanism for the 1,4‐cis‐Butadiene Polymerization: Theoretical Study of Polymerization via Insertion of Butadiene into Al−C Bond with Cationic Gadolinium Metallocene. (Chem. Asian J. 23/2022)

Abstract

A novel mechanism for the polymerization of butadiene by cationic gadolinium metallocene in the presence of excess Al(iBu)3 is presented. The absence of an initial Gd-alkyl bond in this reaction system precludes the conventional mechanism by coordinative chain transfer polymerization (CCTP). Density functional theory (DFT) analysis indicates a mechanism in which cationic Gd assists butadiene insertion into one of the Al–C bonds of Al(iBu)3, explaining the 1,4-cis selectivity unique to this catalytic system. More information can be found in the Research Article by Rika Fukushima et al.