Ontology highlight
ABSTRACT:
SUBMITTER: Pan Z
PROVIDER: S-EPMC2642477 | biostudies-literature | 2008 Jun
REPOSITORIES: biostudies-literature
Pan Zhengzheng Z Horner John H JH Newcomb Martin M
Journal of the American Chemical Society 20080531 25
Rate constants for oxidations of benzyl alcohol-d0 and -d7 by oxoiron(IV) tetramesitylporphyrin radical cation perchlorate in acetonitrile were measured in single turnover kinetic studies. The kinetic isotope effect (kH/kD) increased from 28 at 23 degrees C to 360 at -30 degrees C due to extensive hydrogen atom tunneling that was analyzed in terms of a parabolic energy barrier to tunneling. Similarly, large KIE values were found for oxidations of ethylbenzene-d0 and -d10 at room temperature. The ...[more]