Structures of [CoO(CO<sub>2</sub>)<sub><i>n</i></sub>]<sup>−</sup> and [NiO(CO<sub>2</sub>)<sub><i>n</i></sub>]<sup>−</sup> Clusters Studied by Infrared Spectroscopy

2015-02-05T00:00:00Z (GMT) by Benjamin J. Knurr J. Mathias Weber
We present infrared spectra of [CoO­(CO<sub>2</sub>)<sub><i>n</i></sub>]<sup>−</sup> and [NiO­(CO<sub>2</sub>)<sub><i>n</i></sub>]<sup>−</sup> clusters and interpret them in the framework of computational results employing density functional theory. We find that both [CoO­(CO<sub>2</sub>)<sub><i>n</i></sub>]<sup>−</sup> and [NiO­(CO<sub>2</sub>)<sub><i>n</i></sub>]<sup>−</sup> clusters are generally composed of the same core isomers. The dominant isomers consist of an η<sup>2</sup> CO<sub>2</sub> ligand and a CO<sub>3</sub> moiety that can be bound to the metal atom with monodentate (η<sup>1</sup>) or bidentate (η<sup>2</sup>) connectivity. Minor structural isomers observed are composed of a C<sub>2</sub>O<sub>4</sub> moiety with a lone oxygen atom or a CO<sub>3</sub> unit.