Syndioselective Polymerization of Vinylnaphthalene

Coordination polymerizations of 1‐vinylnaphthalene (1VN), 2‐vinylnaphthalene (2VN) and 6‐methoxy‐2‐vinylnaphthalene (MVN) are carried out at room temperature by using the half‐sandwich scandium precursor FluSiMe 3 Sc(CH 2 SiMe 3 ) 2 (THF) ( 1 ) and the constrained geometry configuration rare‐earth metal precursors FluCH 2 PyLn(CH 2 SiMe 3 ) 2 (THF) n [Flu = C 13 H 8 , Py = C 5 H 4 N; Ln = Sc ( 2a ), n = 0; Ln = Lu ( 2b ), Y( 2c ), n = 1]. Atactic poly(1VN) and perfect syndiotactic poly(2VN) and poly(MVN) are produced by precursors 2a ‐ 2c in a controlled way. Treatment of poly(MVN) with boron tribromide at −20 °C provides a syndiotactic poly(6‐hydroxy‐2‐vinylnaphthalene).