Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr

Kulis, Jakov, Bell, Craig A., Micallef, Aaron S. and Monteiro, Michael J. (2010) Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr. Journal of Polymer Science, Part A: Polymer Chemistry, 48 10: 2214-2223. doi:10.1002/pola.23991

Author Kulis, Jakov
Bell, Craig A.
Micallef, Aaron S.
Monteiro, Michael J.
Title Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr
Journal name Journal of Polymer Science, Part A: Polymer Chemistry   Check publisher's open access policy
ISSN 0887-624X
Publication date 2010-05-15
Sub-type Article (original research)
DOI 10.1002/pola.23991
Volume 48
Issue 10
Start page 2214
End page 2223
Total pages 10
Place of publication Hoboken, NJ, U.S.A.
Publisher John Wiley & Sons
Collection year 2011
Language eng
Formatted abstract
In a previous paper, we described the room temperature rapid, selective, reversible, and near quantitative Cu-activated nitroxide radical coupling (NRC) technique to prepare 3-arm polystyrene stars. In this work, we evaluated the Cu-activation mechanism, either conventional atom transfer or single electron transfer (SET), through kinetic simulations. Simulation data showed that one can describe the system by either activation mechanism. We also found through simulations that bimolecular radical termination, regardless of activation mechanism, was extremely low and could be considered negligible in an NRC reaction. Experiments were carried out to form 2- and 3-arm PSTY stars using two ligands, PMDETA and Me6TREN, in a range of solvent conditions by varying the ratio of DMSO to toluene, and over a wide temperature range. The rate of 2- or 3-arm star formation was governed by the choice of solvent and ligand. The combination of Me6TREN and toluene/DMSO showed a relatively temperature independent rate, and remarkably reached near quantitative yields for 2-arm star formation after only 1 min at 25 °C.
© 2010 Wiley Periodicals, Inc.
Keyword "Click" chemistry
Living radical polymerization
Single electron transfer (SET)
Star polymers
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

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Created: Sun, 23 May 2010, 00:02:12 EST