C−C Bond Formation of Mg‐ and Zn‐Activated Carbon Dioxide

Abstract

Gas-phase activation of CO by chloride tagged metal atoms, [ClM] (M=Mg, Zn), has been investigated by mass spectrometry and high-level quantum chemistry. Both metals activate CO with significant bending of the CO moiety to form complexes with the general formula [ClM,CO ] . The structure of the metal-CO complex depends on the method of formation, and the energy landscapes and reaction dynamics have been probed by collisional induced dissociation and thermal ion molecule reactions with isotopically labeled species. Having established these structural relationships, the gas-phase reactivity of [ClM(κ -O C)] with acetaldehyde (here considered a carbohydrate mimic) was then studied. Formation of lactate and enolate-pyruvate complexes are observed, showing that CO fixation by C-C bond formation takes place. For M=Zn, even formation of free pyruvate ([C H O ] ) is observed. Implications of the observed CO reactivity for the electrochemical conversion of carbon dioxide, and to biochemical and artificial photosynthesis is briefly discussed. Detailed potential energy diagrams obtained by the quantum chemical calculations offer models consistent with experimental observation.

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

“…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.…”

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.…”

Carbon-carbon bond formation in the reaction of hydrated carbon dioxide radical anions with 3-butyn-1-ol

“…C-C bond formation is of key importance for the use of CO2 as C1 building block, and it has been observed in reactions of CO2 •− (H2O)n with methyl acrylate [65] and allyl alcohol [66] as well as in metal-CO2 complexes with acetaldehyde [67].…”