Asymmetric chain‐growth synthesis of polyisocyanide with chiral nickel precatalysts. Issue 16 (5th July 2020)

• Record Type: Journal Article
• Authors: Schraff, Sandra; Kreienborg, Nora M.; Trampert, Jens; Sun, Yu; Orthaber, Andreas; Merten, Christian; Pammer, Frank
• Is Part Of: Journal of polymer science. Volume 58:Issue 16(2020)
• Page Start: 2221
• Page End: 2233
• Publication Date: 2020-07-05
• Subjects: atropisomers -- CD‐spectroscopy, DIPAMP, helical polymers, chain‐growth polymerization -- fulvenes -- nickel catalysts -- polyisocyanides, isocyanides; Polymers -- Periodicals; Polymerization -- Periodicals; Polymerization; Polymers; Periodicals; 547.7
• DOI: 10.1002/pol.20200153
• Languages: English
• ISSNs: 2642-4150

Abstract

Abstract: Nickel(II)‐aryl complexes [(L2 )Ni(Ar)Br] bearing either chiral phosphine ligands (L2 = RR ‐ or SS ‐DIPAMP, Ar = ortho ‐anisyl), or a chiral aryl‐group have been prepared, and their structural optical an chiroptical properties have been characterized. Enantiomeric pairs of both catalysts have been used for the asymmetric polymerization of different isocyanides (M1, M2, M3 ), to give well defined polyisocyanides (P1, P2, P3 ). Their polymerization behavior has been studied, which confirmed chain‐growth polymerization in all cases. The asymmetric induction has been verified by circular dichroism spectroscopy on enantiomeric pairs of all three polymers. Abstract : Helically chiral polyisocyanides have been prepared using different types of Nickel(II) precatalysts via the chain‐growth polymerization. The asymmetric induction has been verified by circular dichroism spectroscopy on enantiomeric pairs of all synthesized polymers. The results demonstrate a versatile approach for the asymmetric synthesis of polyisocyanides.