Chemical transformations of [MAu(PPh)] (M = Pt, Pd) and [Au(PPh)] in methanol induced by irradiation of atmospheric pressure plasma.

The reaction processes of ligand-protected metal clusters induced by irradiating atmospheric pressure plasma (APP) were investigated using optical spectroscopy, mass spectrometry, and density functional theory (DFT) calculations. The target clusters were phosphine-protected gold-based clusters [MAu(PPh)] (M = Pt, Pd) and [Au(PPh)], which have a crown-shaped M@Au (M = Pt, Pd, Au) core with an unligated M site at the central position. The APP irradiation of [MAu(PPh)] (M = Pt, Pd) in methanol resulted in the selective formation of [PtAu(PPh)CO] and [PdAu(PPh)CN] via the addition of a CO molecule and AuCN unit, respectively, generated in situ by the APP irradiation.