Abstract

Platinum carbonyl complexes, Pt +(CO) n , are generated using laser vaporization and probed with infrared photodissociation spectroscopy in the C–O stretching region. No fragmentation is observed for the n = 1–3 complexes, indicative of their high binding energies. Pt +(CO) 4 has enhanced abundance in cluster growth and is difficult to fragment, producing a noisy spectrum. The Pt +(CO) 5,6 complexes fragment efficiently, producing the n = 4 ion. Their spectra, with carbonyl absorptions blue-shifted ∼10 cm −1 with respect to free CO, represent the resonances of Pt +(CO) 4 detected by elimination of weakly bound external ligands. Pt +(CO) 4 is indicated to have filled coordination and a high symmetry structure.

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