Unusual Bonding in Platinum Carbido Clusters

Vibrational spectroscopy and density functional theory calculations are used to determine the structures of small gas-phase platinum carbido dusters PtnC+, n = 3-5. The carbon atom is found to prefer three-coordinate binding sites near the center of the duster, in contrast to most previously investigated adatoms on transition metal clusters. The Pt3C unit is particularly stable, and binding of the carbon atom also leads to significant rearrangement of the metal framework when compared to the bare clusters.