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

Abstract

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 e-caprolactone; in combination with [Ph3C][B(C6F5)4] and AlBu3 i (1 : 1 : 10 molar ratio), these compounds exhibit catalytic activity in the polymerization of isoprene.