Reactivity of [Pt(P(t)Bu(3))(2)] with Zinc(I/II) Compounds: Bimetallic Adducts, Zn–Zn Bond Cleavage, and Cooperative Reactivity

[Image: see text] 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(P(t)Bu(3))(2)] (1) to access Pt/Zn bimetallic complexes. Compounds [(P(t)Bu(3))(2)Pt → Zn(C(6)F(5))(2)] (2) and [Pt(ZnCp*)(6)] (3) (Cp* = pentamethylcyclopentadienyl) were isolated by reactions with Zn(C(6)F(5))(2) and [Zn(2)Cp*(2)], respectively. We also disclose the cooperative reactivity of 1/ZnX(2) pairs (X = Cl, Br, I, and OTf) toward water and dihydrogen, which can be understood in terms of bimetallic frustration.