Mechanistically Guided Predictive Models for Ligand and Initiator Effects in Copper-Catalyzed Atom Transfer Radical Polymerization (Cu-ATRP).

ABSTRACT: Copper-catalyzed atom transfer radical polymerization (Cu-ATRP) is one of the most widely used controlled radical polymerization techniques. Notwithstanding the extensive mechanistic studies in the literature, the transition states of the activation/deactivation of the growing polymer chain, a key equilibrium in Cu-ATRP, have not been investigated computationally. Therefore, the understanding of the origin of ligand and initiator effects on the rates of activation/deactivation is still limited. Here, we present the first computational analysis of Cu-ATRP activation transition states to reveal factors that affect the rates of activation and deactivation. The Br atom transfer between the polymer chain and the Cu catalyst occurs through an unusual bent geometry that involves pronounced intera

SUBMITTER: Fang C 

PROVIDER: S-EPMC6634993 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature