The crucial role of acetonitrile in the mechanism of Pd(II)-catalyzed activation of polar vinyl monomers.

ABSTRACT: The migratory insertion reaction of a polar vinyl monomer into the Pd-alkyl bond and the chain walking process are two of the key steps in the catalytic cycle for the synthesis of functionalized polyolefins through coordination/insertion polymerization. Here, we present a detailed NMR investigation to gain insight into these fundamental steps and demonstrate the critical role of traces of MeCN in this process. We used Pd(II) complexes containing a N-N' bidentate pyridyl-pyridylidene amide (py-PYA) ligand, which are known to cooligomerize ethylene and methyl acrylate (MA). The reaction of three related Pd-(py-PYA) complexes, viz. neutral [Pd(CH₃)Cl(py-PYA)], 1a, and cationic derivatives [Pd(CH₃)(NCCH₃)(py-PYA)][X], X = BArF 1b and PF₆1c, wi

SUBMITTER: Alberoni C 

PROVIDER: S-EPMC11960732 | biostudies-literature | 2025 Apr

REPOSITORIES: biostudies-literature