On the dissociation and conformation of gas-phase methonium ions

The dissociation pathways of both doubly and singly charged methonium ions, (CH(3))(3)N(+) -(CH(2))(n)-(+)N(CH(3))(3)·X(-) (n = 6,10; X = Br, I, and OAc), are measured using blackbody infrared radiative dissociation (BIRD) and SORI-CAD in a Fourier transform mass spectrometer. SORI-CAD of the doubly charged decamethonium ions results primarily in the formation of even electron ions by hydrogen rearrangements. In contrast, homolytic bond cleavage to form two odd electron ions is highly favored in the hexamethonium ion, presumably due to increased Coulomb repulsion in this ion. For BIRD of the singly charged salts, ions are mass selected and dissociated by heating the vacuum chamber to elevated temperatures. Under the low pressure conditions of our experiment, energy is transferred from the chamber walls to the ions by the absorption of blackbody radiation. From the temperature dependence of the unimolecular rate constants for dissociation, Arrhenius activation energies in the zero-pressure limit are obtained. The primary dissociation pathways correspond to counterion substitution reactions which result in loss of N(CH(3))(3) and CH(3)X. For hexamethonium and decamethonium with X = Br or I, the branching ratios for these pathways differ dramatically; the ratio of loss of N(CH(3))(3) and CH(3)Br is 3.8 and 0.4 for hexamethonium and decamethonium bromide, respectively. The hexamethonium acetate salt has a branching ratio of 0.1. The Arrhenius activation energies for hexamethonium (Br or I) and decamethonium (Br or I) are 0.9 and 1.0 eV, respectively. This value for hexamethonium acetate is 0.6 eV. Molecular dynamics simulations and Monte Carlo conformation searching are used to obtain the lowest energy structures of hexamethonium and decamethonium bromide. These calculations indicate that the methonium ion folds around the counterion to form a cyclic salt-bridge structure in which both quaternary nitrogens interact with the oppositely charged counterion. The significantly different branching ratios observed for these ions is attributed to the large change in orientation of the counterion with respect to the ammonium centers as the number of methylene groups in these ions increases. Similar ion conformational differences appear to explain the fragmentation for the OAc counter ion as well.