Photoelectron spectroscopic and computational study of (M-CO2)(-) anions, M = Cu, Ag, Au

In a combined photoelectron spectroscopic and computational study of (M-CO2)(-), M = Au, Ag, Cu, anionic complexes, we show that (Au-CO2)(-) forms both the chemisorbed and physisorbed isomers, AuCO2(-) and Au(-)(CO2), respectively; that (Ag-CO2)(-) forms only the physisorbed isomer, Ag(-)(CO2); and that (Cu-CO2)(-) forms only the chemisorbed isomer, CuCO2(-). The two chemisorbed complexes, AuCO2(-) and CuCO2(-), are covalently bound, formate-like anions, in which their CO2 moieties are significantly reduced. These two species are examples of electron-induced CO2 activation. The two physisorbed complexes, Au(-)(CO2) and Ag(-)(CO2), are electrostatically and thus weakly bound.