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基于哌啶的配体和配合物及其对 rac-丙交酯开环聚合的应用。

Ligands and complexes based on piperidine and their exploitation of the ring opening polymerisation of rac-lactide.

机构信息

Doctoral Training Centre in Sustainable Chemical Technologies, University of Bath, Bath BA2 7AY, UK.

出版信息

Dalton Trans. 2017 Apr 11;46(15):5048-5057. doi: 10.1039/c7dt00751e.

Abstract

A range of ligands based upon 2-(aminomethyl)piperidine have been successfully complexed to Mg(ii), Zn(ii) and group IV metal centres. These complexes have been characterised both in solution and solid state with different coordination geometries realised dependant on the nature of the ligand. For the Mg(ii) and Zn(ii) complexes, M(1-2), were isolated and analysed by DOSY NMR spectroscopy. These ligands also furnished diastereomeric group IV complexes, M(1-2)(OPr). Group IV salalen and salan complexes, M(4-5)(OR) were also found to be diastereomeric in nature, with either β-cis or α-cis geometriesrespectively. The tridentate ligand, 6H, yielded five coordinate complexes with both Ti(iv) and Zr(iv). All complexes were screened for the ring opening polymerisation of rac-lactide under both solvent and melt conditions. For the Mg(ii) and Zn(ii) complexes, good activity was observed with Zn(1-2) demonstrating immortal polymerisation characteristics.

摘要

一系列基于 2-(氨甲基)哌啶的配体已成功地与 Mg(ii)、Zn(ii)和 IVB 族金属中心配位。这些配合物在溶液和固态中都得到了表征,不同的配位几何结构取决于配体的性质。对于 Mg(ii)和 Zn(ii)配合物,M(1-2),通过 DOSY NMR 光谱法进行了分离和分析。这些配体还提供了非对映异构体的 IVB 族配合物,M(1-2)(OPr)。IVB 族的 salalen 和 salan 配合物,M(4-5)(OR),也被发现具有非对映异构体性质,分别具有 β-顺式或 α-顺式几何构型。三齿配体 6H,与 Ti(iv)和 Zr(iv)生成了五配位配合物。所有配合物都在溶剂和熔体条件下对 rac-丙交酯的开环聚合进行了筛选。对于 Mg(ii)和 Zn(ii)配合物,Zn(1-2)表现出了不朽的聚合特性,显示出了良好的活性。

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