Wade A. Braunecker

TL;DR: In this article, a review of recent mechanistic developments in the field of controlled/living radical polymerization (CRP) is presented, with particular emphasis on structure-reactivity correlations and "rules" for catalyst selection in ATRP, for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerisation (SFRP), including organic and transition metal persistent radicals.

TL;DR: In this paper, the concept of initiators for continuous activator regeneration (ICAR) in atom transfer radical polymerization (ATRP) is introduced, whereby a constant source of organic free radicals works to regenerate the CuI activator, which is otherwise consumed in termination reactions when used at very low concentrations.

TL;DR: Equilibrium constants in Cu-based atom transfer radical polymerization (ATRP) were determined for a wide range of ligands and initiators in acetonitrile at 22 degrees C and excellent correlations of the equilibrium constants with the Cu(II/I) redox potentials and the carbon-halogen bond dissociation energies were observed.

TL;DR: In this paper, a single-electron-transfer living radical polymerization (SET-LRP) was proposed to produce alkyl halide radical anion intermediates via outer-sphere electron transfer.

TL;DR: In this article, a thermodynamic scheme representing the atom transfer radical polymerization (ATRP) equilibrium as the formal sum of equilibria involving carbon−halogen bond homolysis and three additional distinct thermodynamic contributions related to the catalyst is rigorously evaluated.