title: Primary kinetic isotope effects on hydride transfer from heterocyclic compounds to NAD(+) analogues.
abstract: Primary kinetic isotope effects (KIEs), k(H)/k(D), have been determined spectrophotometrically for the reactions of NAD(+) analogues (acridinium ions, 1a-e(+), and quinolinium ion, 2(+)) with heteroaromatic compounds such as 3-methyl-2-phenylbenzothiazoline, 3H(D), and 1,3-dimethyl-2-phenylbenzimidazoline, 4H(D) in a mixed solvent containing four parts 2-propanol and one part water at 25.0 +/- 0.1 degrees C. The KIEs decrease from 6.24 to 3.93 as the equilibrium constant, K, is increased from about 1 to 10(12) by the structural variation in the hydride acceptor. The Marcus theory of atom transfer in a linear, triatomic model of the reaction, with tunneling, can explain the variation of KIE with K. The Marcus theory is based on a model involving no high-energy intermediates, leading to a one-step mechanism. The present system satisfies this condition.
authors.affiliation: Department of Science Education, Kangwon National University, Chunchon 200-701, Korea.
authors.forename: Hyun Joo
authors.initials: HJ
authors.lastname: Kil
authors.forename: In-Sook Han
authors.initials: IS
authors.lastname: Lee