Infrared Spectroscopy of Gas-Phase M(CO) (M = Co, Rh, Ir) Ion-Molecule Complexes.

The structures of gas-phase M(CO) (M = Co, Rh, Ir; n = 2-15) ion-molecule complexes have been investigated using a combination of infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy and density functional theory. The results provide insight into fundamental metal ion-CO interactions, highlighting the trends with increasing ligand number and with different group 9 ions. Spectra have been recorded in the region of the CO asymmetric stretch around 2350 cm using the inert messenger technique and their interpretation has been aided by comparison with simulated infrared spectra of calculated low-energy isomeric structures. All vibrational bands in the smaller complexes are blue-shifted relative to the asymmetric stretch in free CO, consistent with direct binding to the metal center dominated by charge-quadrupole interactions. For all three metal ions, a core [M(CO)] structure is identified to which subsequent ligands are less strongly bound. No evidence is observed in this size regime for complete activation or insertion reactions.