3 years ago

Highly 2,3-Selective Polymerization of Phenylallene and Its Derivatives with Rare-Earth Metal Catalysts: From Amorphous to Crystalline Products

Highly 2,3-Selective Polymerization of Phenylallene and Its Derivatives with Rare-Earth Metal Catalysts: From Amorphous to Crystalline Products
Dongmei Cui, Zhaohe Liu, Fei Lin, Tiantian Wang
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 AliBu3, 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. Rare-earth metal complexes (Flu-CH2-Py)Ln(CH2SiMe3)2(THF)n (Ln=Sc, Lu, Tm, Y and Gd), upon the activation of [Ph3C][B(C6F5)4] and AliBu3, were employed to catalyze the 2,3-selective polymerization of phenylallene (PA) and its derivatives bearing polar or nonpolar substituent groups. Owing to the highly regular backbones, most obtained polymers were crystalline, thus being the first crystalline polymers based on allene derivatives.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201707601

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