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- Title
Highly 2,3-Selective Polymerization of Phenylallene and Its Derivatives with Rare-Earth Metal Catalysts: From Amorphous to Crystalline Products.
- Authors
Lin, Fei; Liu, Zhaohe; Wang, Tiantian; Cui, Dongmei
- Abstract
Rare-earth metal complexes (Flu-CH2-Py)Ln(CH2SiMe3)2(THF) n (Ln=Sc( 1), Lu( 2), Tm( 3), Y( 4) and Gd( 5)), upon the activation of [Ph3C][B(C6F5)4] and Al iBu3, 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.
- Subjects
RARE earth metal catalysts; POLYMERIZATION; METAL complexes; ALLENE; AMORPHOUS substances
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 46, p14845
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201707601