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Abstract <p>The La(III) bis(amidinate) amido complex {2-[Ph<sub>2</sub>Р(O)]C<sub>6</sub>H<sub>4</sub>NC(Bu<sup><i>t</i></sup>)N(2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)}<sub>2</sub>LaN(SiMe<sub>3</sub>)<sub>2</sub> (<b>I</b>) was synthesized by the reaction of 2-[Ph<sub>2</sub>Р(O)]C<sub>6</sub>H<sub>4</sub>NHC(Bu<sup><i>t</i></sup>)=N(2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) (HL) and La[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>3</sub> in 2 : 1 molar ratio and isolated in 74% yield. X-ray analysis revealed that in <b>I</b> both monoanionic amidinate ligands are κ<sup>3</sup>-N,N,O-coordinated to La(III) ion. Complex <b>I</b> demonstrates high catalytic activity in ring-opening polymerization of cyclic esters and enables 100% conversion of 100–300 equiv of <i>rac</i>-lactide in 30 min or 100–500 equiv of ε-caprolactone in 1 min providing highly controlled polymerization. The obtained polymeric samples feature linear dependence of molecular weight vs. the monomer loading and rather narrow polydispersity (<i>M</i><sub>w</sub>/<i>M</i><sub><i>n</i></sub> = 1.36–1.88).</p>

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Lanthanum Bis(amidinate) Amido Complex {2-[Ph2Р(O)]C6H4NC(But)N(2,6-Me2C6H3)}2LaN(SiMe3)2: Synthesis, Structure, and Catalytic Activity in Ring-Opening Polymerization of rac-Lactide and ε-Caprolactone

  • 期刊论文

  • 发表日期：

    2025年5月1日

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  • A. O. Tolpygin,
  • A. V. Cherkasov,
  • G. K. Fukin,
  • A. A. Trifonov

摘要

Abstract

The La(III) bis(amidinate) amido complex {2-[Ph2Р(O)]C6H4NC(But)N(2,6-Me2C6H3)}2LaN(SiMe3)2 (I) was synthesized by the reaction of 2-[Ph2Р(O)]C6H4NHC(But)=N(2,6-Me2C6H3) (HL) and La[N(SiMe3)2]3 in 2 : 1 molar ratio and isolated in 74% yield. X-ray analysis revealed that in I both monoanionic amidinate ligands are κ3-N,N,O-coordinated to La(III) ion. Complex I demonstrates high catalytic activity in ring-opening polymerization of cyclic esters and enables 100% conversion of 100–300 equiv of rac-lactide in 30 min or 100–500 equiv of ε-caprolactone in 1 min providing highly controlled polymerization. The obtained polymeric samples feature linear dependence of molecular weight vs. the monomer loading and rather narrow polydispersity (Mw/Mn = 1.36–1.88).