Charge-Dependent Trends in Structures and Vibrational Frequencies of [CO-Au-O2]q (q = −1, 0, +1) Complexes: Evidence for Cooperative Interactions

Abstract

Charge-dependent trends in the structures, vibrational frequencies, and binding energies of binary [AuCO](q) and [AuO(2)](q) and ternary [O(2)AuCO](q) complexes (q = -1,0,+1), have been investigated using density functional theory calculations. Three different geometrical motifs, given descriptive names of "separated", "pre-reactive", and "long-range", are identified for the ternary complexes. For the binary systems, the general trend is that the complexes become more diffuse as the charge becomes more negative, having longer intermolecular bond distances and weaker binding energies. The trends shown by the ternary complexes are more complicated, and are different for the various geometrical motifs. However, a general trend is that there is a cooperative interaction involving both the CO and O(2) with the Au center, which becomes more pronounced as the negative charge on the complexes increases from cationic to neutral to anionic. This cooperative interaction leads to increased electron density on the O(2) moiety, as is reflected in the bond-lengths and vibrational frequencies. Furthermore, it is found that for the pre-reactive complexes, the role of the Au center is to stabilize the formation of a conjugated π-system between the CO and O(2) molecules.