期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 53, 期 35, 页码 9226-9230出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201403643
关键词
iso-selectivity; lactide; lanthanum; lutetium; ring-opening polymerization
资金
- EPSRC [EP/K014070/1, EP/K035274/1]
- Engineering and Physical Sciences Research Council [EP/C544838/1, EP/C544846/1, EP/K035274/1] Funding Source: researchfish
- EPSRC [EP/K035274/1] Funding Source: UKRI
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.
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