title: Joint theoretical experimental investigation of the electron spin resonance spectra of nitroxyl radicals: application to intermediates in in situ nitroxide mediated polymerization (in situ NMP) of vinyl monomers.
abstract: Density functional theory (DFT) calculations have been performed to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated hyperfine coupling constants (HFCCs) to experimental data for a set of linear and cyclic alkylnitroxyl radicals. Considering this tested approach, the nature of different nitroxides has been predicted or confirmed for (a) the reaction of C-phenyl- N- tert-butylnitrone and AIBN, (b) N- tert-butyl-alpha-isopropylnitrone and benzoyl peroxide, (c) tert-butyl methacrylate polymerization in the presence of sodium nitrite as mediator, and (d) for the reaction of a nitroso compound with AIBN. Values of HFCC experimentally determined have been confirmed by DFT calculations.
authors.affiliation: Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, Namur, Belgium.
authors.forename: Natalia
authors.initials: N
authors.lastname: Zarycz
authors.forename: Edith
authors.initials: E
authors.lastname: Botek
authors.forename: Benoît
authors.initials: B
authors.lastname: Champagne
authors.forename: Valérie
authors.initials: V
authors.lastname: Sciannaméa
authors.forename: Christine
authors.initials: C
authors.lastname: Jérôme
authors.forename: Christophe
authors.initials: C
authors.lastname: Detrembleur