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

Thomas Junkers*, Christopher Barner-Kowollik, Michelle L. Coote

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    19 Citations (Scopus)

    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.

    Original languageEnglish
    Pages (from-to)1891-1898
    Number of pages8
    JournalMacromolecular Rapid Communications
    Volume32
    Issue number23
    DOIs
    Publication statusPublished - 1 Dec 2011

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