13C kinetic isotope effects in the copper(I)-mediated living radical polymerization of methyl methacrylate
Related Experiment Video
Updated: Sep 29, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Simon Harrisson1, Jonathan P Rourke, David M Haddleton
1Department of Chemistry, University of Warwick, Coventry, UK CV4 7AL.
Abstract:
Carbon-13 kinetic isotope effects (KIEs) have been determined for free-radical and copper-mediated living radical polymerizations of methyl methacrylate at 60 degrees C. While free-radical polymerization shows only one primary 13C KIE, on the least-substituted double bond carbon (k12/k13 = 1.045), two significant KIEs are observed, one on each double bond carbon, for copper-mediated polymerization (k12/k13(H2C=) = 1.050, k12/k13(=C <) = 1.010), showing that copper-mediated living radical polymerization does not propagate via a simple free radical process.
Related Concept Videos
Free-Radical Chain Reaction and Polymerization of Alkenes
Radical Chain-Growth Polymerization: Mechanism
Radical Reactivity: Concentration Effects
Radical Reactivity: Intramolecular vs Intermolecular
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Radical Reactivity: Steric Effects
Along with electronic factors, steric factors also account...
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
