Formation of Heterobimetallic Complexes by Addition of d10-Metal Ions to cis-[(dppe)M(?C-2-C6F4PPh2)2] (M = Ni, Pd, and Pt)

Abstract

The reactivity of [(dppe)M(κC-2-C6F4PPh2)2] (M = Ni (1Ni), Pd (1Pd), and Pt (1Pt); dppe = 1,2-bis(diphenylphosphino)ethane)) toward monovalent coinage metal ions (M′ = Cu, Ag, and Au) has been investigated. Two main isomers [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] (2PdAg, 2PdAu, 2PtCu, 2PtAg, and 2PtAu) and [(dppe)M(μ-2-C6F4PPh2)2M′Cl] (3PdCu, 3PdAg, and 3PtCu) could be detected. Quantum chemical calculations underpin the enhanced thermodynamic stability of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] for combinations of the heavier metals. NBO calculations reveal attractive Pt···Cu and Pt···Ag interactions in complexes 2PtCu and 2PtAg, respectively. From the reaction of [(dppe)M(κC-2-C6F4PPh2)2] with an excess of [AuCl(tht)], a series of trinuclear complexes [(dppe)M(μ-2-C6F4PPh2)2(AuCl)2] (4NiAu2, 4PdAu2, and 4PtAu2) was prepared. Reaction of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] with TlPF6 leads to the formation of cationic derivatives [(dppe)M(μ-2-C6F4PPh2)2M′]PF6 with P–M′–P (6PtAu) or P–M′–C (7PdAu, 7PtAu) bonding situations around the coinage metal.