H2, B-H, and Si-H Bond Activation and Facile Protonolysis Driven by Pt-Base Metal Cooperation

We report a series of heterobimetallic Pt/Zn and Pt/Ca complexes to study the effect of proximity of a dicationic base metal on the organometallic Pt species. Varying degrees of Pt center dot center dot center dot Zn and Zn interaction with the bridging Me group are achieved, showcasing snapshots of a hypothetical process of retrotransmetalation from Pt to Zn. In contrast, only weak interactions were observed for Ca with a Pt-bound Me group. Activation of H-2, B-H and Si-H bonds leads to the formation of hydride-bridged Pt-H-Zn complexes, which is not observed in the absence of Zn, pointing out the importance of metal-metal cooperation. Reactivity of PtMe2/M2+ with terminal acetylene, water and methanol is also studied, leading to facile protonation of one of the Me groups at the Pt center only when Zn is present. This study sheds light on various ways in which the presence of a 2+ metal cation significantly affects the reactivity of a common organo-platinum complex.