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Highly 2,3‐Selective Polymerization of Phenylallene and Its Derivatives with Rare‐Earth Metal Catalysts: From Amorphous to Crystalline Products
Author(s) -
Lin Fei,
Liu Zhaohe,
Wang Tiantian,
Cui Dongmei
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201707601
Subject(s) - allene , polymerization , selectivity , metal , chemistry , rare earth , catalysis , polymer , amorphous solid , polymer chemistry , medicinal chemistry , crystallography , stereochemistry , organic chemistry , mineralogy
Rare‐earth metal complexes (Flu‐CH 2 ‐Py)Ln(CH 2 SiMe 3 ) 2 (THF) n (Ln=Sc( 1 ), Lu( 2 ), Tm( 3 ), Y( 4 ) and Gd( 5 )), upon the activation of [Ph 3 C][B(C 6 F 5 ) 4 ] and Al i Bu 3 , were employed to catalyze the polymerization of allene derivatives under mild conditions. The Gd, Y, Tm, Lu metal based precursors exhibited distinguished 2,3‐selectivity (>99.9 %) for phenylallene (PA) polymerization, whereas the smallest Sc metal based precursor showed a moderate 2,3‐selectivity. The activity increased with the central metal size following the trend of Gd( 5 )>Tm( 4 )>Y( 3 )>Lu( 2 )>Sc( 1 ). Moreover, Gd( 5 ) also realized the purely 2,3‐selective polymerizations of polar or nonpolar allene derivatives, para ‐methylphenylallene, para ‐flourophenylallene and para ‐methoxyphenylallene, regardless of electron‐donating or ‐withdrawing substituents. Owing to the highly regular backbones, these polymers (except PPA) were crystalline, thus being the first crystalline polymers based on allene derivatives.