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Effect of the Penultimate Unit on the CON Bond Homolysis in SG1‐Based Alkoxyamines
Author(s) -
Bertin Denis,
Dufils PierreEmmanuel,
Durand Isabelle,
Gigmes Didier,
Giovanetti Bruno,
Guillaneuf Yohann,
Marque Sylvain R. A.,
Phan Trang,
Tordo Paul
Publication year - 2008
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200700441
Subject(s) - homolysis , chemistry , unit (ring theory) , macromolecule , polymer chemistry , organic chemistry , radical , psychology , biochemistry , mathematics education
Abstract The effect of the penultimate unit on the CON bond homolysis rate constant k d was studied for model alkoxyamines. It was shown that the k d for fragments containing penultimate and antepenultimate units were nicely predicted by the tri‐parametric relationship developed in Macromolecules 2005 , 38 , 2638 and Eur. J. Org. Chem . 2006 , 7 , 1755 (log k d = −14.33 + 15.06 × σ RS + 20.00 × σ I + 6.96 × υ ). A striking effect was observed only for a tert ‐butyl‐like group as the penultimate unit.