Issue 25, 2020

Cationic indium catalysts for ring opening polymerization: tuning reactivity with hemilabile ligands

Abstract

This is a comprehensive study of the effects of rationally designed hemilabile ligands on the stability, reactivity, and change in catalytic behavior of indium complexes. We report cationic alkyl indium complexes supported by a family of hemi-salen type ligands bearing hemilabile thiophenyl (2a), furfuryl (2b) and pyridyl (2c) pendant donor arms. Shelf-life and stability of these complexes followed the trend 2a < 2b < 2c, showing direct correlation to the affinity of the pendant donor group to the indium center. Reactivity towards polymerization of epichlorohydrin and cyclohexene oxide followed the trend 2a > 2b > 2c with control of polymerization following an inverse relationship to reactivity. Surprisingly, 2c polymerized racemic lactide without an external initiator, likely through an alkyl-initiated coordination-insertion mechanism.

Graphical abstract: Cationic indium catalysts for ring opening polymerization: tuning reactivity with hemilabile ligands

Supplementary files

Article information

Article type
Edge Article
Submitted
03 Mar 2020
Accepted
13 Apr 2020
First published
22 Apr 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 6485-6491

Cationic indium catalysts for ring opening polymerization: tuning reactivity with hemilabile ligands

C. Goonesinghe, H. Roshandel, C. Diaz, H. Jung, K. Nyamayaro, M. Ezhova and P. Mehrkhodavandi, Chem. Sci., 2020, 11, 6485 DOI: 10.1039/D0SC01291B

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