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

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 ¹H 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.