Vibrational Characterization of Radical Ion Adducts between Imidazole and CO₂

We address the molecular level origins of the dramatic difference in the catalytic mechanisms of CO₂ activation by the seemingly similar molecules pyridine (Py) and imidazole (Im). This is accomplished by comparing the fundamental interactions of CO₂ radical anions with Py and Im in the isolated, gas phase PyCO₂^- and ImCO₂^- complexes. These species are prepared by condensation of the neutral compounds onto a (CO₂) _n^- cluster ion beam by entrainment in a supersonic jet ion source. The structures of the anionic complexes are determined by theoretical analysis of their vibrational spectra, obtained by IR photodissociation of weakly bound CO₂ molecules in a photofragmentation mass spectrometer. Although the radical PyCO₂^- system adopts a carbamate-like configuration corresponding to formation of an N-C covalent bond, the ImCO₂^- species is revealed to be best described as an ion-molecule complex in which an oxygen atom in the CO₂^- radical anion is H-bonded to the NH group. Species that feature a covalent N-C interaction in ImCO₂^- are calculated to be locally stable structures, but are much higher in energy than the largely electrostatically bound ion-molecule complex. These results support the suggestion from solution phase electrochemical studies (Bocarsly et al. ACS Catal. 2012, 2, 1684-1692) that the N atoms are not directly involved in the catalytic activation of CO₂ by Im.