Skip to Main content Skip to Navigation
New interface
Journal articles

Intramolecular proton transfer (IPT) in alkoxyamine: a theoretical investigation

Abstract : The Intramolecular Proton Transfer (IPT) in alkoxyamines is one of the main factors determining the process of Nitroxide Mediated Polymerization (NMP). Recently, we proposed an experimental approach to study IPT and applied it to a series of alkoxyamines. It was found that IPT dramatically depends on the structure of the alkoxyamine, but it was not clear which factors are significant for IPT (M. V. Edeleva et al., J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 6579-6595). To understand the mechanism and the factors determining the IPT process, in this article we investigate the geometrical parameters and thermokinetics of this reaction using the BMK/6-311++G(3df,3pd)//B3LYP/6-31+G(d,p) method. It was found that the thermokinetics and geometrical parameters of the transition state (TS) for IPT do not depend on the alkoxyamine structure. The only factor which determines the occurrence of IPT is the position of the TS energy level of the C-ON bond homolysis.
Document type :
Journal articles
Complete list of metadata
Contributor : Didier Siri Connect in order to contact the contributor
Submitted on : Monday, December 12, 2016 - 6:49:44 PM
Last modification on : Tuesday, December 14, 2021 - 8:42:06 AM




Dmitriy Parkhomenko, Elena G. Bagryanskaya, Sylvain R.A. Marque, Didier Siri. Intramolecular proton transfer (IPT) in alkoxyamine: a theoretical investigation. Physical Chemistry Chemical Physics, 2013, 15 (33), pp.13862--13871. ⟨10.1039/c3cp50821h⟩. ⟨hal-01415178⟩



Record views