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((PBu3)-Bu-t)(2)] (1) to access Pt/Zn bimetallic complexes. Compounds [((PBu3)-Bu-t)(2)Pt -> 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.

Automated summary

Metal-only Lewis pairs based on zinc electrophiles are of interest in Negishi cross-coupling reactions. This study explores the use of sterically hindered [Pt((PBu3)-Bu-t)(2)] (1) to access Pt/Zn bimetallic complexes, resulting in the isolation of unique compounds with different reactivity. The cooperative reactivity of 1/ZnX2 pairs (X = Cl, Br, I, and OTf) towards water and dihydrogen is also disclosed, demonstrating bimetallic frustration.