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Mono(boratabenzene) rare-earth metal dialkyl complexes: synthesis, structure and catalytic behaviors for styrene
Xiufang Wang1, Xuebing Leng, Yaofeng Chen
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China. yaofchen@mail.sioc.ac.cn.
Abstract:
Four mono(boratabenzene) rare-earth metal dialkyl complexes, [(3,5-Me2-C5H3BR)Ln(CH2SiMe3)2(THF)] (1: R = NEt2, Ln = Sc; 2: R = NEt2, Ln = Lu; 3: R = Ph, Ln = Sc; 4: R = Ph, Ln = Lu), were synthesized efficiently via a one-pot strategy with Li[3,5-Me2-C5H3BR] (R = NEt2, Ph), LnCl3(THF)x (Ln = Sc, x = 3; Ln = Lu, x = 0), and LiCH2SiMe3. The solid-state structures of 1 and 2 were determined by single-crystal X-ray diffraction. Variable-temperature NMR studies indicated that the energy barrier for the rotation of aminoboratabenzene in 1 (ΔG‡ ≈ 71 kJ mol−1) is higher than that of phenylboratabenzene in 3 (ΔG‡ ≈ 59 kJ mol−1). These mono(boratabenzene) rare-earth metal dialkyl complexes’ catalytic behaviors for styrene polymerization were investigated, and found that mono(boratabenzene) scandium dialkyl complexes show high catalytic activities for syndiotactic polymerization upon activation with cocatalysts.
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