Well‐Controlled Living Polymerization of N‐Propargylamides and Their Derivatives by Rhodium Catalysis

Abstract

A substantially improved method for living polymerization of N‐propargylamides and their derivatives has been developed. Rhodium(I) complexes bearing an aryl‐substituted 1,3,5‐hexatriene chain can work as excellent initiators of the polymerization of such non‐conjugated terminal alkynes to give the corresponding cis‐stereoregular polymers having a narrow molecular weight distribution. The typical living nature has been confirmed by investigating the effects of initial feed ratios of the monomer to the initiator on the molecular weight of the resulting polymers as well as multistage polymerization. Moreover, we demonstrated that the present method enables functionalization of both polymer chain ends and synthesis of novel block copolymers consisting of poly(N‐propargylamide) and poly(phenylacetylene) blocks with a narrow molecular weight distribution.

Stereoregular polymerization of phenylacetylene using alkynyl and methyl rhodium(i) complexes with functionalized phosphine ligands: linear vs. branched poly(phenylacetylene)s

“…13 Living polymerization allows the control of the polymer molecular weight, the modification of polymer chain ends, and the synthesis of block polymers with well-defined architectures. [14][15][16][17] In this context, molecular Rhalkynyl, Rh-vinyl [18][19][20] and Rh-aryl [21][22][23] complexes enable the controlled polymerization of PA derivatives to give highly stereoregular polymers with narrow molecular weight distributions and very high initiation efficiencies. The first controlled stereospecific polymerization of PAs using a wellcharacterized group 9 metal complex was reported by Noyori and co-workers using the pentacoordinated alkynyl rhodium(I) catalyst [Rh(CuCPh)(nbd)(PPh 3 ) 2 ] and DMAP (4-(dimethylamino)pyridine) as the co-catalyst.…”

Synthesis Methodology of End-Functionalized Poly(quinolylene-2,3-methylene)s: Living Cyclocopolymerization Using Aryl Palladium Initiators Conveniently Prepared from Versatile Aryl Halide

“…One method for synthesizing end functional polymers is the introduction of a functional group derived from the initiator (α-chain end) (Figure a). The method is based on living polymerization (e.g., radical, − ionic, , and coordination polymerizations − ), which is practical and efficient because substituents can be reliably introduced into the α-chain end unless a chain transfer reaction occurs. However, it is necessary to prepare an initiator for each substituent and examine the reaction conditions for each initiator.…”

Chiroptical and colorimetric switches based on helical polymer-metal nanocomposites preparedviaredox metal translocation of helical polymer metal complexes

“…To overcome this obstacle, it is necessary to explore other helical macromolecules to decorate MNPs. In this sense, stimuli-responsive synthetic helical polymers 12–48 are excellent candidates to prepare helical polymer-MNP nanocomposites where the two chiralities of the helix can be explored in different fields. From the literature, it is known that the main limitation of the use of dynamic helical polymers as coating agents to prepare helical polymer-MNP nanocomposites is the functional group used to link the macromolecule to the metal nanoparticle.…”