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Small platinum cluster hydrides in the gas phase.

The reactions of small cationic platinum clusters (Pt2(+)-Pt7(+)) with molecular hydrogen were investigated, and the structures of the hydride complexes were analyzed using IR spectroscopy. We determined the relative reaction rates for the addition of the first H2 molecule to the platinum clusters, and we report the hydrogen saturation coverages observed at high H2 concentration. High H atom per Pt atom ratios were observed, similar to earlier measurements on other group-10 transition metals. The structures of the fully saturated complexes of Pt2(+)-Pt5(+) were investigated using a combination of infrared multiple-photon dissociation (IR-MPD) spectroscopy in the frequency range of 550-2050 cm(-1) and density functional theory-based calculations. We found molecularly bound hydrogen alongside bridge and often atop binding of hydrogen atoms for all of the low-energy structures, in contrast to earlier theoretical predictions.