title: Electrospray ionization mass spectrometric investigation of ammonium ion complexes with anomeric 2,3-O-isopropylidene-1alpha- and -1beta-D-ribofuranosyl azides: anomeric and kinetic isotope effects in ammonium affinities.
abstract: [Methanol + ammonium acetate] solutions of anomeric 2,3-O-isopropylidene-1alpha- and 1beta-ribofuranosyl azides were investigated by electrospray ionization mass spectrometry (ESI-MS). The compounds included d6-labeled and/or unlabeled isopropylidene groups that enable the identification of peaks characteristic of the ammonium-attached monomeric (MNH4(+)), ammonium-bound homodimeric ([M]2NH4(+)) and heterodimeric ([MNH4M1](+)) complex ions in ESI mass spectra of solutions of a pair of compounds. The intensities of the product ion peaks obtained by the collisionally activated ammonium-bound dimeric ions are related to the secondary isotope effect k(alpha)/k(alphad6) = 0.88 and k(beta)/k(betad6) = 1.25 or to isotope plus anomeric effects k(alpha)/k(betad6) = 1.43 and k(beta)/k(alphad6) = 0.59 in the ammonium affinities of these compounds. The calculations of solely anomeric effects in the ammonium affinities of alpha and beta anomeric compounds obtained from the data presented previously give two series of values: k(alpha)/k(beta) = (k(alpha)/k(alphad6))(k(alphad6)/k(beta)) = 1.49 and k(alphad6)/k(betad6) = (k(alphad6)/k(beta))(k(beta)/k(betad6)) = 2.12 or k(alpha)/k(beta) = (k(alpha)/k(betad6))(k(betad6)/k(beta)) = 1.14 and k(alphad6)/k(betad6) = (k(alphad6)/k(alpha))(k(alpha)/k(betad6)) = 1.63. The disparities of these results indicate the different structures of hydrogen bonding in ammonium-bound dimeric complexes which decompose to monomeric ions with different rate constants. Comparison of experimental results obtained by the qualitative approach of the kinetic method and ammonium affinities of these compounds calculated by the semi-empirical molecular orbital method (AM1) show that the [MNH4M1](+) dimeric complex ions dissociate to the most stable MNH4(+) and M1NH4(+) monomeric ions. The obtained relative order of ammonium affinities of these compounds is: alphad6 > alpha > beta > betad6.
authors.affiliation: Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia. b.kralj@ijs.si
authors.forename: Bogdan
authors.initials: B
authors.lastname: Kralj
authors.forename: Darko
authors.initials: D
authors.lastname: Kocjan
authors.forename: Joze
authors.initials: J
authors.lastname: Kobe