Metal-Size Influence in Iso-Selective Lactide Polymerization

被引：162
作者：
Bakewell, Clare [1 ]
White, Andrew J. P. [1 ]
Long, Nicholas J. [1 ]
Williams, Charlotte K. [1 ]
机构：
[1] Imperial Coll London, Dept Chem, South Kensington, England
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 35期
基金：
英国工程与自然科学研究理事会;
关键词：
iso-selectivity; lactide; lanthanum; lutetium; ring-opening polymerization; RING-OPENING POLYMERIZATION; YTTRIUM PHOSPHASALEN INITIATORS; RAC-LACTIDE; RACEMIC LACTIDE; CYCLIC ESTERS; ALUMINUM COMPLEXES; INDIUM CATALYST; STEREOSELECTIVE POLYMERIZATION; STEREOCOMPLEX FORMATION; BIS(PHENOLATO) LIGANDS;
D O I：
10.1002/anie.201403643
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Iso-selective initiators for the ring-opening polymerization (ROP) of rac-lactide are rare outside of Group 13. We describe the first examples of highly iso-selective lutetium initiators. The phosphasalen lutetium ethoxide complex shows excellent iso-selectivity, with a P-i value of 0.81-0.84 at 298 K, excellent rates, and high degrees of polymerization control. Conversely, the corresponding La derivative exhibits moderate heteroselectivity (P-s= 0.74, 298 K). Thus, the choice of metal center is shown to be crucial in determining the level and mode of stereocontrol. The relative order of rates for the series of complexes is inversely related to metallic covalent radius: that is, La> Y> Lu.
引用
收藏
页码：9226 / 9230
页数：5
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