Computational Evaluation of the Sulfonyl Radical as a Universal Leaving Group for RAFT Polymerisation*
Ganna Gryn’ova A , Tamaz Guliashvili B D , Krzysztof Matyjaszewski C and Michelle L. Coote A D
+ Author Affiliations
- Author Affiliations
A Australian Research Council Centre of Excellence for Free Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
B General Electric Power and Water, Water and Process Technologies, 4636 Somerton Road, Trevose, PA 19053, USA.
C Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA.
D Corresponding authors. Email: tamazguliasvili@yahoo.com; mcoote@rsc.anu.edu.au
Australian Journal of Chemistry 66(3) 308-313 https://doi.org/10.1071/CH12452
Submitted: 1 October 2012 Accepted: 31 October 2012 Published: 17 December 2012
Abstract
The present study investigates the performance of the sulfonyl radical, i.e. •SO2Ph, as a universal leaving group in reversible addition–fragmentation chain-transfer (RAFT) polymerisation. The sulfonyl radical is widely used as a radical initiator and has already been proved successful as a leaving group in an atom-transfer radical polymerisation. Our results, obtained using high-level ab initio computational methodology under relevant experimental conditions, indicate superior performance of the sulfonyl compared with a reference cyanoisopropyl group in controlling RAFT of a wide range of monomers. Importantly, the presence of sulfonyl chain ends in the polymers so formed opens attractive possibilities for further functionalisation. Potential synthetic routes to the R-sulfonyl RAFT agents are discussed.
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