Competition of Proton and Electron Transfers in Gas‐Phase Reactions of Hydrogen‐Containing Dications CHX²⁺ (X=F, Cl, Br, I) with Atoms, Nonpolar and Polar Molecules

Abstract

The competition between proton and electron transfer in reactions of mass-selected dications CHX2+ (X = F, Cl, Br, and I) with rare gas atoms (Ne, Ar, Kr, and Xe) and selected molecular reagents (N2, O2, CO, H2O, and HCl) is studied in the gas phase. In the ion-molecule reactions of CHX2+ dications with atoms and nonpolar molecules, it is the energy balance of electron transfer that acts as the decisive factor: when the exothermicity of electron transfer exceeds 2 eV, this process predominates at the expense of bond-forming proton transfer. In marked contrast, the reactions between these triatomic dications and polar molecules are governed for the benefit of the thermochemically more favored products resulting from proton transfer.

Formation of Organoxenon Dications in the Reactions of Xenon with Dications Derived from Toluene

“…The ions C 7 H 7 + , Xe + , and XeH + have the same onset as the parent ion and peak at about E lab = 0 eV, which is behavior characteristic for exothermic or thermoneutral ion/molecule reactions via an intimate collision complex. [17,21] The curve for the dicationic product C 7 H 6 Xe 2 + has a similar shape, but the maximum is shifted by about 1 eV. Whereas the general energy behavior of this channel also implies the involvement of a collision complex, the formation of C 7 H 6 Xe 2 + thus appears to be favored by a small amount of excess energy.…”

“…[16] 4) Proton transfer from the dication to xenon according to Reaction (6) is a typical process of hydrogen-containing dications. [17] The …”

Silicon Compounds of Neon and Argon

“…The vertical scale refers to the precursor dication with an intensity of 1.00 (off-scale); note the different scaling compared to Figure 1. The small remaining signal at m/z 43.0 in the gray trace is either due to a small amount of 29 SiF 3 2+ co-selected with the first quadrupole, or to residual neon in the analyzer from the previous experiment. Inset in (a) shows a neutral-gain spectrum of the SiF 3…”

Siliciumverbindungen von Neon und Argon

“…Die bei hohen Stoßenergien verschwindende Ausbeute an ArSiF 2 2+ erklärt auch, warum frü-here Studien diesen Reaktionskanal nicht auffinden konnten. [23] Diese experimentellen Befunde werden von der quantenchemischen Behandlung von Reaktion (1) [19] Der Einschub in (a) zeigt das Neutralzuwachsspektrum [20,21] der SiF 3 2+ -Isotope mit einer Massenverschiebung des zweiten Analysators von Dm = 10.5 amu, was dem bei U oct = 2 V gebildeten Produkt-Ion [8][9][10][11][12][13][14][15]22,29] sodass vergleichbare Strategien in der Zukunft zu weiteren neuen Edelgasverbindungen führen könnten. [30] Eingegangen am …”