Issue 6, 2019

AliBu3: unprecedented main-group metal catalyst for helical sense-selective polymerization of chiral aryl isocyanides and copolymerization with achiral aryl isocyanides

Abstract

The polymerization of isocyanide in screw-sense usually proceeds via a late-transition metal-catalyzed coordination-insertion mechanism or a metal-free cation-initiated carbocationic mechanism. By contrast, less attention has been paid to main-group metal catalysts in isocyanide polymerization, and no main-group metal catalyst has exhibited high activity and helical sense selectivity in isocyanide polymerization till date. In the presence of [Ph3C][B(C6F5)4], AliBu3, which is a commercially available, cheap, simple and common main-group organometallic reagent, represents the first example of a highly efficient single-site main-group metal catalyst for the polymerization of several aryl isocyanides bearing polar, chiral and tetraphenylethylene (TPE) substituents, showing very high activities up to 3.6 × 106 g polymer molact.−1 h−1. Moreover, this catalytic system also catalyzes the homopolymerization of chiral isocyanides and the copolymerization between chiral isocyanides and achiral isocyanides in screw-sense to form high molecular weight polyisocyanides with varying degrees of single-handed helical conformation and AIE nature. Based on in situ1H NMR, IR, and ESI-MS spectroscopy, a cationic Al alkyl active species and a possible coordination-insertion (co)polymerization mechanism are proposed.

Graphical abstract: AliBu3: unprecedented main-group metal catalyst for helical sense-selective polymerization of chiral aryl isocyanides and copolymerization with achiral aryl isocyanides

Supplementary files

Article information

Article type
Research Article
Submitted
07 4 2019
Accepted
20 4 2019
First published
22 4 2019

Mater. Chem. Front., 2019,3, 1192-1198

AliBu3: unprecedented main-group metal catalyst for helical sense-selective polymerization of chiral aryl isocyanides and copolymerization with achiral aryl isocyanides

X. Wu, X. Yan, Z. Yang, S. Zhang, X. Li, Y. Dong and J. Zhi, Mater. Chem. Front., 2019, 3, 1192 DOI: 10.1039/C9QM00218A

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