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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.

organometallics

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