Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 35, Pages 9226-9230Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201403643
Keywords
iso-selectivity; lactide; lanthanum; lutetium; ring-opening polymerization
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Funding
- 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
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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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