Cooperative bonding interactions of various oxygen species on the IB group metal anions

Abstract

Series of MOx− (M = Cu, Ag, and Au; x = 1–3) complexes and one solitary kind of AgO5− were generated using a magnetron sputter cluster source, and their reactions with additional O2 were studied by combining a low temperature flow reactor and a time-of-flight mass spectrometer. The structures and bonding characters of these complexes were explored according to the observed reaction channels and systematic DFT calculations, in which OAgO−, OAg(η1-O2)−, and (η1-O3)Ag (η1-O2)− were newly observed complexes. The structure (η1-O3)Ag (η1-O2)− was further confirmed using the molecule tagging infrared photodissociation spectroscopy. The theoretical binding energies of oxygen species in MOx− (M = Cu, Ag, and Au; x = 1–3, and 5) are consistent with the experimental observations, which clearly show a cooperative effect of bonding interactions of various oxygen species on the Cu, Ag and Au anions. The contributions of (n-1)d, ns, and np components of the IB metals to their bonding interactions were discussed, which account for the above cooperative effect as well as the much stronger Cu–O bonds than corresponding Ag–O and Au–O bonds in MOx−.