Revealing model dependencies in "assessing the RAFT equilibrium constant via model systems: An EPR study"

Junkers, T., Barner-Kowollik, C., & Coote, M. L. (2011) Revealing model dependencies in "assessing the RAFT equilibrium constant via model systems: An EPR study". Macromolecular Rapid Communications, 32(23).

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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. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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14 citations in Web of Science®
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ID Code: 99275
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :13
Export Date: 5 September 2016
CODEN: MRCOE
Correspondence Address: Junkers, T.; Polymer Reaction Design Group, Institute for Materials Research (IMO), Universiteit Hasselt, B-3590-Diepenbeek, Belgium; email: thomas.junkers@uhasselt.be
Chemicals/CAS: Polymers
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Keywords: ab initio quantum mechanical calculations, intermediate radical termination, kinetics (polymer), model dependency, rate coefficients, reversible addition fragmentation transfer (RAFT), Intermediate radical terminations, Quantum-mechanical calculation, Reversible addition-fragmentation transfers, Calculations, Chemical bonds, Equilibrium constants, Quantum chemistry, Quantum theory, Uncertainty analysis, polymer, article, synthesis, Polymers
DOI: 10.1002/marc.201100494
ISSN: 10221336
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 05 Oct 2016 03:37

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