title: Homolysis of N-alkoxyamines: a computational study.
abstract: During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO*, the reversible formation of N-alkoxyamines [P-ON(R1)R2] reduces significantly the concentration of polymer radicals (P*) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the C-ON(R1)R2 bond. In this study, theoretical BDEs of a large series of model N-alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (Tc), and the dissociation rate constant (k(d)), of the N-alkoxyamines are established. The homolytic cleavage of the N-OC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N-alkoxyamines with a O-C-ON(R1)R2 fragment, and the strengthening of their C-ON(R1)R2 bond is interpreted in terms of stabilizing anomeric interactions.
authors.affiliation: UMR-CNRS 6517, Universités d'Aix-Marseille 1 et 3, Faculté des Sciences de St-Jérôme, Case 521, 13397 Marseille Cedex 20 (France).
authors.forename: Anouk
authors.initials: A
authors.lastname: Gaudel-Siri
authors.forename: Didier
authors.initials: D
authors.lastname: Siri
authors.forename: Paul
authors.initials: P
authors.lastname: Tordo