Triketiminate bis(borohydride) complexes of rare-earth metals [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y, Nd): synthesis, structure, and catalytic activity in polymerization of rac-lactide, ε-caprolactone, and isoprene

被引:0
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作者
G. G. Skvortsov
A. V. Cherkasov
A. A. Trifonov
机构
[1] Russian Academy of Sciences,G. A. Razuvaev Institute of Organometallic Chemistry
[2] Russian Academy of Sciences,A. N. Nesmeyanov Institute of Organoelement Compounds
来源
Russian Chemical Bulletin | 2017年 / 66卷
关键词
rare-earth metals; triketiminate ligand; borohydride ligand; synthesis; structure; catalysis; isoprene; lactide; polymerization;
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摘要
A new triketimine (2,6-Me2C6H3N=CMe)2CH(2,6-Me2C6H3N=CBut) (1) was synthesized by the reaction of imidoyl chloride 2,6-Me2C6H3N=CClBut with lithium diketiminate (2,6-Me2C6H3N=CMe)2CHLi. In the crystalline state, compound 1 exists in the diimineenamine form; in solution, in the triimine form. The metalation of triketimine 1 with n-butyllithium in THF at 0 °C produced lithium triketiminate [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Li(THF)2 (2). The metathesis reactions of Ln(BH4)3(THF)3 (Ln = Y, Nd) with compound 2 (1: 1 molar ratio, THF) gave the neutral triketiminate bis(borohydride) complexes [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y (3), Nd (4)). As opposed to the complexes with neutral triketimine, the monoanionic triketiminate ligand is coordinated to Li and Y or Nd cations in a bidentate fashion. Complexes 3 and 4 catalyze the polymerization of rac-lactide and ε-caprolactone; in combination with [Ph3C][B(C6F5)4] and AlBu3i (1 : 1 : 10 molar ratio), these compounds exhibit catalytic activity in the polymerization of isoprene.
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页码:1665 / 1674
页数:9
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