The activation of carbon dioxide by first row transition metals (Sc–Zn)

Abstract

The activation of CO2 by chloride-tagged first-row transition metal anions [ClM]− (M = Sc–Zn), was examined by mass spectrometry, quantum chemical calculations, and statistical analysis.

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

“…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.…”

“…It is well established that metal atoms and anions may add CO 2 to form complexes in gas phase reactions, formally metal carbonites (MCO 2 ). Their preferred structures are shown in Scheme , which in the case of alkali and alkaline earth metals is the bidentate coordination of the metal to both oxygen atoms (κ 2 -O 2 C), − while for transition metals, the metal typically binds to the carbon atom (η 1 -CO 2 ) or in a side-on fashion (η 2 -CO 2 ). − Early transition metals, M = Sc, Ti, V, and Cr, ,,− even insert into one of the C–O bonds with subsequent CO elimination: …”

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.…”

Infrared Multiple Photon Dissociation Spectroscopy of Hydrated Cobalt Anions Doped with Carbon Dioxide CoCO2(H2O)n−, n=1–10, in the C−O Stretch Region

“…The same is true in a salt environment where the interaction with positive charge centers is responsible for the stabilization . In the interaction of CO 2 with metal ions, electron transfer from the metal to the electrophilic carbon atom can occur spontaneously, leading to complexes of the metal center with CO 2 − . When a single bond is formed between the metal and the carbon atom, as observed for example, with the nickel group, coinage metal, or bismuth anions, the excess charge in this metalloformate η 1 ‐(C) complex, MCO 2 − , is delocalized over the whole molecular ion …”

“…[15,16] In the interaction of CO 2 with metal ions, electront ransfer from the metal to the electrophilic carbon atom can occur spontaneously,l eadingt oc omplexes of the metal centerw ith CO 2 À . [4,[17][18][19][20] When as ingle bond is formed between them etal and the carbon atom, as observed for example,w ith the nickel group, coinage metal, or bismuth anions, the excess chargei nt his metalloformate h 1 -(C) complex, MCO 2 À ,i sd elocalized over the whole molecular ion. [21,22] Organometallic complexes of transition metals like cobalt can play an important role in catalytic reductionso fC O 2 , [23] a key step in carbon capturea nd usage (CCU) processes.…”