Bond Formation with Maintenance of Twofold Charge: Generation of C₂O₃²⁺ in the Reaction of CO₂²⁺ with CO₂

Abstract

100 years after the prediction of the existence of C2O3 by Berthelot, doubly charged C2O32+ has been identified as a product in the reaction of CO22+ with CO2 (see scheme). The occurrence of this reaction for such a small dication indicates that bond‐forming processes might play a much larger role in reactions of dications than has been anticipated to date.

Bond-Forming Chemistry in the Gas-Phase Reactions of Atomic and Molecular Dications and Trications

“…[59][60][61][62] The integrating nature of the GIB experiments, where all the product ions can be collected regardless of their scattering angle, also makes these experiments intrinsically more sensitive than crossed-beam experiments and, thus, perhaps the methodology of choice for detecting weak dicationic reactions. 54,55,63 Such sensitivity comes, in principle, at the expense of the angular scattering information, and the associated insight into the reaction dynamics, that a crossed-beam experiment provides. However, ingenious use of pulsed reactant beams, coupled with measurements of the TOF of reaction products to the detector, has in fact allowed considerable insights into reaction dynamics to be gleaned from GIB experiments.…”

“…Using a collision cell contained within an ion guide ensures that 'sideways-scattered' products are not lost, as they can be in a crossed-beam experiment, and reliable measurements of the number of product ions formed can be made. 54,55 In addition, and simultaneously, the depletion in the flux of the reactant dications following the interaction with the neutrals can also be determined. As explained in the succeeding text, these characteristics of the GIB experiment make this arrangement ideal for investigating the kinetics of dication reactions.…”

Superelectrophilic chemistry in the gas phase

“…For example, in the reaction of CO 2 2+ with CO 2 , a "hot" intermediate C 2 O 4 2+ is formed, the cooling step is accomplished by the elimination of an oxygen atom, and, finally, the dicationic product C 2 O 3 2+ can be observed [15]. In comparison to other dications, however, the bond-forming reactions of hydrocarbon dications are more often reported.…”

Electron transfer and bond-forming reactions following collisions of I2+with CO and CS2

“…[9] In parallel with these studies of dicationic electron transfer, laboratory studies have also revealed that molecular dications can take part in bond-forming reactivity at low collision energies in the centre-of-mass frame. [11,14,20,22,[28][29][30][31][32][33][34][35][36][37][38][39] Indeed, it has been shown that gas-phase dication chemistry can provide new pathways for the formation of specific bonds and unusual compounds. [35,40] Focusing on atomic dications, the reactive species in the current study, there has been considerable attention paid to the bond-forming chemistry of metal atom dications; such investigations were stimulated, in part, by an attempt to rationalise the activity of heterogeneous catalysts.…”