A Theoretical Study on the Reactivity and Charge Effect of PtRu Clusters toward Methanol Activation

Density functional theory (DFT) calculations were performed to gain mechanistic insight into the methanol C-H and O-H bond activations mediated by ruthenium-doped platinum cationic clusters [PtnRum](+) (m + n = 3, n >= 1). The charge effect on the reactivity has been elucidated. Calculations show that positive charge is evenly distributed on the three Pt atoms of the [Pt-3](+) cluster, while in the Ru-doped clusters, positive charge is mainly distributed on the Ru atom(s). The reactivity of [PtnRum](+) is significantly greater than neutral [PtnRum] during the initial C-H bond cleavage, while only [Pt-3](+) exhibits greater reactivity than [Pt-3] in the course of O-H bond cleavage. This study may aid in deeper understanding of C-H/O-H bond activations mediated by metal clusters.