Reactivity of [Pt(PtBu3)2] with Zinc(I/II) Compounds: Bimetallic Adducts, Zn–Zn Bond Cleavage, and Cooperative Reactivity

Metal-only Lewis pairs (MOLPs) based on zinc electrophiles are particularly interesting due to their relevance to Negishi cross-coupling reactions. Zinc-based ligands in bimetallic complexes also render unique reactivity to the transition metals at which they are bound. Here we explore the use of sterically hindered [Pt­(PtBu3)2] (1) to access Pt/Zn bimetallic complexes. Compounds [(PtBu3)2Pt → Zn­(C6F5)2] (2) and [Pt­(ZnCp*)6] (3) (Cp* = pentamethylcyclopentadienyl) were isolated by reactions with Zn­(C6F5)2 and [Zn2Cp*2], respectively. We also disclose the cooperative reactivity of 1/ZnX2 pairs (X = Cl, Br, I, and OTf) toward water and dihydrogen, which can be understood in terms of bimetallic frustration.