Infrared Photodissociation Spectra of Mass‐Selected Homoleptic Dinuclear Palladium Carbonyl Cluster Cations in the Gas Phase

Abstract

AbstractInfrared spectra of mass‐selected homoleptic dinuclear palladium carbonyl cluster cations Pd2(CO)n+ (n=5–8) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Pd2(CO)5+ cation is characterized to have two weakly semibridging CO groups with C2 symmetry. The Pd2(CO)6+ and Pd2(CO)7+ cations are determined to involve one weakly semibridging CO group. The Pd2(CO)8+ cation is a CO coordination saturated cluster, which is determined to have a D2d structure with all of the carbonyl groups terminally bonded. Bonding analysis indicates that these cluster cations each has a PdPd half bond. The PdPd distance increases with the number of CO ligands.