Formation of [PtPd2(μ3-X)2(P–P)(dppmX)2]2+ (X = S, Se; P–P = dppe, 2 × PPh3) aggregates through activation of the chalcogen-rich [PtX4] ring by a PdI–PdI bond

Abstract

Redox addition of the Pd–Pd bond in [Pd₂Cl₂(dppm)₂] across S–S or Se–Se bond in [Pt(X₄-κ²X¹,X⁴)(P–P)] (X = S, Se; P–P = dppe or 2 × PPh₃; dppm = bis(diphenylphosphino)methane, dppe = bis(diphenylphosphino)ethane) leads to the isolation of [PtPd₂(μ₃-X)₂(P–P)(dppmX-κ²X,P⁴)₂]²⁺ and represents an atom-economy process that converts chalcogen-rich complexes to heterometallic chalcogenide aggregates. Activation of the [PtX₄] ring is achieved by tetrachalcogenide reduction and dual oxidation of palladium and phosphine.