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

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

Journal

Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084

Output data

Year: 2013, Volume: 15, Number: 33, Pages: 13862-13871 Pages count : 10 DOI: 10.1039/c3cp50821h

Authors

Parkhomenko Dmitriy ^1,2 , Bagryanskaya Elena G. ^1,3 , Marque Sylvain R.A. ⁴ , Siri Didier ⁴

Affiliations

1	(Данные Web of science) Int Tomog Ctr SB RAS, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
3	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Novosibirsk 630090, Russia
4	(Данные Web of science) Aix Marseille Univ, CNRS ICR UMR 7273, F-13397 Marseille 20, France

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.

Parkhomenko D. , Bagryanskaya E.G. , Marque S.R.A. , Siri D.
Intramolecular proton transfer (IPT) in alkoxyamine: a theoretical investigation
Physical Chemistry Chemical Physics. 2013. V.15. N33. P.13862-13871. DOI: 10.1039/c3cp50821h WOS Scopus РИНЦ

Web of science	WOS:000322517800018
Scopus	2-s2.0-84881260561
Elibrary	20452827
OpenAlex	W1983977549