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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/13095

Title: Revealing Model Dependencies in "Assessing the RAFT Equilibrium Constant via Model Systems: An EPR Study"
Authors: Junkers, Thomas
Barner-Kowollik, Christopher
Coote, Michelle L.
Issue Date: 2011
Abstract: In a recent article (W. Meiser, M. Buback, Assessing the RAFT Equilibrium Constant via Model Systems: An EPR Study, Macromol. Rapid Commun. 2011, 18, 1490-1494), it is claimed that evidence is found that unequivocally proves that quantum mechanical calculations assessing the equilibrium constant and fragmentation rate coefficients in dithiobenzoate-mediated reversible addition fragmentation transfer (RAFT) systems are beset with a considerable uncertainty. In the present work, we show that these claims made by Meiser and Buback are beset with a model dependency, as a critical key parameter in their data analysis the addition rate coefficient of the radicals attacking the C=S double bond in the dithiobenzoate induces a model insensitivity into the data analysis. Contrary to the claims made by Meiser and Buback, their experimental results can be brought into agreement with the quantum chemical calculations if a lower addition rate coefficient of cyanoisopropyl radicals (CIP) to the CIP dithiobenzoate (CPDB) is assumed. To resolve the model dependency, the addition rate coefficient of CIP radicals to CPDB needs to be determined as a matter of priority.
Notes: [Junkers, Thomas] Univ Hasselt, Inst Mat Res IMO, Polymer React Design Grp, B-3590 Diepenbeek, Belgium. [Barner-Kowollik, Christopher] KIT, Inst Tech Chem & Polymerchem, D-76128 Karlsruhe, Germany. [Coote, Michelle L.] Australian Natl Univ, Res Sch Chem, ARC Ctr Excellence Free Rad Chem & Biotechnol, Canberra, ACT 0200, Australia.
URI: http://hdl.handle.net/1942/13095
DOI: 10.1002/marc.201100494
ISI #: 000298098100003
ISSN: 1022-1336
Category: A1
Type: Journal Contribution
Validation: ecoom, 2013
Appears in Collections: Research publications

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