Characterization of the alkali metal oxalates (MC₂O₄⁻) and their formation by CO₂ reduction via the alkali metal carbonites (MCO₂⁻)

Abstract

The reduction of carbon dioxide to oxalate has been studied by experimental Collisionally Induced Dissociation (CID) and vibrational characterization of the alkali metal oxalates, supplemented by theoretical electronic structure calculations.

Computational Exploration of the Direct Reduction of CO2 to CO Mediated by Alkali Metal and Alkaline Earth Metal Chloride Anions

“…13−19 Early transition metals, M = Sc, Ti, V, and Cr, 14,15,20−29 was observed for M = Li but not for M = Na−Cs. 12 It turned out that the same type of decarbonylation had previously been seen by other authors. 30−32…”

“…The degree of charge transfer from the metal to CO 2 during complexation is a useful metric for the activation of the latter. 12,13,22 Our NBO analysis, outlined in Table 1B, suggests that while CO 2 receives almost two electrons from the alkaline earth metal chlorides, the alkalis The reactivity trends are similar as for the reduction of one CO 2 to CO. The same reasoning applies for the relative stabilities of the carbonate products as the oxides, and the reactions of Li − and BeCl − can conveniently be used to illustrate this once more.…”

“…Consequently, we will only need to consider [M,CO 2 ] − intermediates with intact CO 2 cores, consistent with previously published literature on reactions between these metals and CO 2 . [4][5][6][7][8][9]11,12 The formation of the intermediate metal carbonites 39,40 1A/ 1B via a weakly bonded ion−molecule complex INC1 is always exothermic and facile. Small or negligible barriers separate INC1 from 1A and 1B, respectively.…”

Organometallic Gas‐phase Ion Chemistry and Catalysis: Insights Into the Use of Metal Catalysts to Promote Selectivity in the Reactions of Carboxylic Acids and Their Derivatives

“…Given the numerous MS-based studies on organometallic ion chemistry related to catalysis, the scope of this review is limited to metal-catalyzed transformations of carboxylic acids and their derivatives of relevance to organic synthesis. Fragmentation reactions of coordinated carboxylates that involve redox chemistry and give rise to metal anions (Curtis et al, 2010(Curtis et al, , 2011Attygalle, Axe, & Weisbecker, 2011;Butson, Curtis, & Mayer, 2016) or metal-CO 2 complexes (Dossmann et al, 2012;Rodriguez-Blanco et al, 2013;Miller et al, 2014;Blaziak et al, 2018;Jestila & Uggerud, 2018;Miller & Uggerud, 2018;Jestila et al, 2020), although fascinating in their own right, are not reviewed. Carboxylic acids and their derivatives that contain multiple functional groups (e.g., peptides and proteins) are not considered.…”

Interactions of CO2 Anion Radicals with Electrolyte Environments from First-Principles Simulations

“…The shorter coordination distance and/or more decreased bond angle of CO 2 – indicate that the intermediate complex can be present for prolonged periods and likely undergo subsequent desired reactions such as chelation, charge transfer interactions, and bond cleavage/formation reactions. 48 , 49 We further construct a physics-based model to rationalize the relative contributions of electrostatic and covalent/noncovalent interactions to the stabilization effects of CO 2 – .…”