title: Remarkable effects of chirality on deslipping reactions of diastereomeric rotaxanes and relevant mechanism involving pre-equilibrium.
abstract: The first clear differentiation on deslipping rates affected by the difference in the diastereomeric stereocenters of rotaxanes up to 8.4 times and unexpectedly large steric kinetic isotope effect on the deslipping reaction (ca. 20%) were observed. On the basis of the kinetic parameters, steric kinetic isotope effect, and (1)H NMR spectra of the nondeuteriated and deuteriated rotaxanes, we propose a deslipping mechanism involving pre-equilibrium.
authors.affiliation: Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 563-8531, Japan. hirose@chem.es.osaka-u.ac.jp
authors.forename: Keiji
authors.initials: K
authors.lastname: Hirose
authors.forename: Yamato
authors.initials: Y
authors.lastname: Nakamura
authors.forename: Yoshito
authors.initials: Y
authors.lastname: Tobe
mesh_terms: D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D043862:Rotaxanes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D043862:Rotaxanes