Abstract

We present infrared photodissociation spectra of [Co(CO2)n](-) ions (n = 3-11) in the wavenumber region 1000-2400 cm(-1), interpreted with the aid of density functional theory calculations. The spectra are dominated by the signatures of a core ion showing bidentate interaction of two CO2 ligands with the Co atom, each forming C-Co and O-Co bonds. This structural motif is very robust and is only weakly affected by solvation with additional CO2 solvent molecules. The Co atom is in oxidation state +1, and both CO2 ligands carry a negative charge.

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