Formation of heterobinuclear Pt–Au complexes by chelate ring-opening of cis-[Pt(κ2-C6R4PPh2)2] (R = H, F)

•Establishment of a new method for the preparation of heterobinuclear metal complexes.•Ring-opening in cis-[Pt(ĸ2-C6R4PPh2)2] and preparation of bimetallic compounds.•Difference in reactivity between cis and trans isomers of platinum compounds.•The preferential reactivity of the cis-over trans-isomers of [Pt(κ2-C6R4PPh2)2].

Mixed metal complexes of the type [Pt(κ2-2-C6R4PPh2) (PPh3) (μ-2-C6R4PPh2)AuCl] (R = H, F) can be prepared by treatment of cis-[Pt(κ2-C6R4PPh2)2] with [AuCl(PPh3)]. Under similar reaction conditions, the trans isomer of [Pt(κ2-C6F4PPh2)2] is unreactive. Computational studies have been performed to provide insights into the reasons for this difference in reactivity. Density Functional Theory (DFT) calculations show that formation of an AuCl adduct of [Pt(κ2-2-C6R4PPh2)2] is favoured over nucleophilic addition of PPh3 to Pt as the initial step of the reaction, and reveal the required energy of the cis and trans isomers of the bis-chelate [Pt(κ2-2-C6R4PPh2)2] in forming the mixed metal Pt–Au compounds. NBO analysis sheds more light on the bonding orbitals of the cis and trans isomers, suggesting that the Pt–P bonds in the cis isomer are more labile.

Graphical abstractA new way of preparing heteronuclear bimetallic species.Figure optionsDownload full-size imageDownload as PowerPoint slide