TY - JOUR
T1 - Joint theoretical experimental investigation of the electron spin resonance spectra of nitroxyl radicals
T2 - Application to intermediates in in situ nitroxide mediated polymerization (in situ NMP) of vinyl monomers
AU - Zarycz, Natalia
AU - Botek, Edith
AU - Champagne, Benoît
AU - Sciannaméa, Valérie
AU - Jérôme, Christine
AU - Detrembleur, Christophe
PY - 2008/8/28
Y1 - 2008/8/28
N2 - 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-pnenyl-N-tert-butylnitrone and AIBN, (b) N-tert-butyl-α-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.
AB - 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-pnenyl-N-tert-butylnitrone and AIBN, (b) N-tert-butyl-α-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.
UR - http://www.scopus.com/inward/record.url?scp=51849136593&partnerID=8YFLogxK
U2 - 10.1021/jp803552x
DO - 10.1021/jp803552x
M3 - Article
AN - SCOPUS:51849136593
SN - 1520-6106
VL - 112
SP - 10432
EP - 10442
JO - Journal of physical chemistry B
JF - Journal of physical chemistry B
IS - 34
ER -