Boron-Catalyzed Polymerization of Dienyltriphenylarsonium Ylides: On the Way to Pure C5 Polymerization

Xin Wang; Nikos Hadjichristidis

doi:10.1002/anie.202015217

Boron-Catalyzed Polymerization of Dienyltriphenylarsonium Ylides: On the Way to Pure C5 Polymerization

Angew Chem Int Ed Engl. 2021 Apr 6;60(15):8431-8434. doi: 10.1002/anie.202015217. Epub 2021 Mar 1.

Authors

Xin Wang¹, Nikos Hadjichristidis¹

Affiliation

¹ Physical Sciences and Engineering Division, KAUST Catalysis Center, Polymer Synthesis Laboratory, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955, Saudi Arabia.

Abstract

The first C5 polymerization is reported, where the main-chain is growing by five carbon atoms of the monomer at a time. Three dienyltriphenylarsonium ylide monomers were synthesized and polymerized with triethylborane as an initiator, leading to random terpolymers (C1, C3, C5) with mainly C5 repeating units (up to 84.1 %). It has been found that the methyl group (electron-donating substituent) on the conjugated double bond of the ylides facilitates the formation of C5 segments. A mechanism was proposed based on NMR characterization and DFT calculations. The high C5 content ensures that things are on the right track for pure C5 homopolymerization.

Keywords: arsonium; boranes; polymers; reaction mechanisms; ylides.