Reactions of Copper and Silver Cations with Carbon Dioxide: An Infrared Photodissociation Spectroscopic and Theoretical Study

Abstract

The reaction of copper and silver cations with carbon dioxide was studied by mass-selected infrared photodissociation spectroscopy. Quantum chemical calculations were performed on these products, which aided the experimental assignments of the infrared spectra and helped to elucidate the geometrical and electronic structures. The Cu and Ag cations bind to an oxygen atom of CO in an end-on configuration via a charge-quadrupole electrostatic interaction in the [M(CO)] complexes. The formation of oxide-carbonyl and carbonyl-carbonate structures is not favored for the interaction of CO with Cu and Ag. For n = 3 and 4, the n + 0 structure is preferred. [Note on the nomenclature: Using i + j, i denotes the number of CO molecules in the first coordination shell, and j denotes the number of CO molecules in the second coordination shell.] The two nearly energy-identical n + 0 and (n - 1) + 1 structures coexist in n = 5 and 6. While the six-coordinated structure is favored for [Cu(CO)], the n + 0 configuration is dominated in [Ag(CO)]. The reaction of CO with the cationic metal atoms has been compared to that with the neutral and anionic metal atoms, which would have important implications for understanding the interaction of CO with reduction catalysts and rationally designing catalysts for CO reduction based on cost-effective transition metals.

Electron-Induced Decomposition of Different Silver(I) Complexes: Implications for the Design of Precursors for Focused Electron Beam Induced Deposition

“…This effect may be akin to the uptake of CO 2 by Ag(I) 3,3-dimethyl-1-butynyl, as discussed in Section 3.1 . In line with a previous theoretical study [ 55 ], we tentatively propose that Ag + ions remaining in the sublimate layer after electron-induced fragmentation of Ag(I) 2,2-dimethylbutanoate react with CO 2 from the ambient atmosphere upon handling in air. When resuming electron irradiation, this additional CO 2 is released in addition to that produced from the remaining intact Ag(I) compound.…”

Covalent Bonding Between Be+and CO2in BeOCO+with a Surprisingly High Antisymmetric OCO Stretching Vibration

“…In contrast, the CO 2 molecule was only weakly bound to the metal cations, exclusively in an end-on configuration via electrostatic charge-quadrupole interaction, resulting in a linear M + OCO structure. − The antisymmetric CO 2 stretching vibrations in these cationic complexes are generally blue-shifted with respect to the free CO 2 molecule. − It was found that these blue-shifted vibrations vary only slightly from one system to another due to electrostatic interaction. − Here we report the generation of the cationic metal complex BeOCO + , which exhibits an antisymmetric CO 2 stretching mode at 2418.9 cm –1 in solid neon, blue-shifted by 71 cm –1 with respect to free CO 2 . The observed value is the highest antisymmetric CO 2 stretching frequency ever reported for a carbon dioxide complex. − …”

IR spectroscopic characterization of the co-adsorption of CO2 and H2 onto cationic Cun+ clusters

“…7 IR spectroscopic studies have aimed to obtain structural insight into the solvent-driven activation of CO 2 by various metal cations. [37][38][39][40][41][42][43][44][45][46][47] The general picture that emerges is that metal cations mostly bind CO 2 molecules intact, in end-on configuration via one of the oxygen atoms through quadrupole-related electrostatic interactions.…”