The DOI matches its Crossref record; 19 of the 19 references it cites were found in a registry or an index.
Mechanism of Living Lactide Polymerization by Dinuclear Indium Catalysts and Its Impact on Isoselectivity
Abstract
A family of racemic and enantiopure indium complexes 1-11 bearing bulky chiral diaminoaryloxy ligands, H(NNO(R)), were synthesized and fully characterized. Investigation of both the mono- and the bis-alkoxy-bridged complexes [(NNO(R))InX](2)[μ-Y][μ-OEt] (5, R = (t)Bu, X = Y = Cl; 8, R = Me, X = I, Y = OEt) by variable temperature, 2D NOESY, and PGSE NMR spectroscopy confirmed dinuclear structures in solution analogous to those obtained by single-crystal X-ray crystallography. The dinuclear complexes in the family were highly active catalysts for the ring-opening polymerization (ROP) of lactide (LA) to form poly(lactic acid) (PLA) at room temperature. In particular, complex 5 showed living polymerization behavior over a large molecular weight range. A detailed investigation of catalyst stereoselectivity showed that, although (R,R/R,R)-5 is highly selective for l-LA, only atactic PLA is obtained in the polymerization of racemic LA. No such selectivity was observed for complex 8. Importantly, the selectivities obtained for the ROP of racemic LA with (R,R/R,R)-5 and (R,R/R,R)-8 are different and, along with kinetics investigations, suggest a dinuclear propagating species for these complexes.
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Cites
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Cited by
Bakewell, C., Cao, T.-P.-A., Long, N., Le Goff, X. F., Auffrant, A., & Williams, C. K. (2012) · Journal of the American Chemical Society · doi:10.1021/ja310003v · Cited by 226
Gallium and indium complexes for ring-opening polymerization of cyclic ethers, esters and carbonates
Dagorne, S., Normand, M., Kirillov, E., & Carpentier, J.-F. (2013) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2013.02.012 · Cited by 215
Metal‐Size Influence in Iso‐Selective Lactide Polymerization
Bakewell, C., White, A. J. P., Long, N. J., & Williams, C. K. (2014) · Angewandte Chemie International Edition · doi:10.1002/anie.201403643 · Cited by 178
Dinuclear catalysts for the ring opening polymerization of lactide
Kremer, A. B., & Mehrkhodavandi, P. (2019) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2018.09.008 · Cited by 152
Self-citationPang, X., Duan, R., Li, X., Hu, C., Wang, X., & Chen, X. (2018) · Macromolecules · doi:10.1021/acs.macromol.7b02662 · Cited by 100
Metadata
- Authors
- Yu, I., Acosta-Ramírez, A., & Mehrkhodavandi, P.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-07-18
- Volume
- 134
- Issue
- 30
- Pages
- 12758-12773
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2284071100
- Cited by
- 184
- References
- 19
- FWCI
- 8.54
- Type
- journal article
- Language
- en
- Open access
- closed
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