Intramolecular kinetic isotope effect in hydride transfer from dihydroacridine to a quinolinium ion. Rejection of a proposed two-step mechanism with a kinetically significant intermediate

Org Biomol Chem. 2008 Sep 21;6(18):3349-53. doi: 10.1039/b806869k. Epub 2008 Jul 28.

Abstract

The intramolecular kinetic isotope effect (KIE) for hydride transfer from 10-methyl-9,10-dihydroacridine to 1-benzyl-3-cyanoquinolinium ion has been found to be 5-6 by both (1)H NMR and mass spectrometry. This KIE is consistent with other hydride transfers. It is inconsistent with the high intermolecular KIEs derived by fitting to a two-step mechanism with a kinetically significant intermediate complex, and it is inconsistent with the strong temperature dependence of those KIEs. We therefore reject the two-step mechanism for this reaction, and we suggest that other cases proposed to follow this mechanism are in error.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Acridines / chemistry*
  • Hydrogen / chemistry*
  • Ions / chemistry
  • Isotopes / chemistry
  • Kinetics
  • Magnetic Resonance Spectroscopy
  • Molecular Structure
  • Quinolinium Compounds / chemistry*

Substances

  • Acridines
  • Ions
  • Isotopes
  • Quinolinium Compounds
  • Hydrogen