Formation of heterobimetallic complexes by addition of d(10)-metal Ions to cis-[(dppe)M(kappa C-2-C6F4PPh2)(2)] (M = Ni, Pd, and Pt)

The reactivity of [(dFFe)M(kappa C-2-C6F4PPh2)(2)] (M = Ni (1Ni), Pd (1Pd), and Pt (lPt); dppe = 1,2-bis(diphenylphosphino)ethane)) toward monovalent coinage metal ions (M' = Cu, Ag, and Au) has been investigated. Two main isomers adppe)M(kappa C-2-C6F4PPh2)(mu-2-C6F4PPh2)M'Cl] (2PdAg, 2PdAu, 2PtCu, 2PtAg, and 2PtAu) and [(dppe)M(mu-2-C6F4PPh2)(2)M'Cl] (3PdCu, 3PdAg, and 3PtCu) could be detected. Quantum chemical calculations underpin the enhanced thermodynamic stability of [(dppe)M(kappa C-2-C6F4PPh2)(mu(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(kappa C-2-C6F4PPh2)(2)] with an excess of [AuCI(tht)], a series of trinuclear complexes [(dPpe)M(mu-2-C6F4PPh2)(2).(AuCI)(2)] (4NiAu(2), 4PdAu(2), and 4PtAu(2)) was prepared. Reaction of [(dppe)M(kappa C-2-C6F4PPh2)(mu-2C(6)F(4)PPh(2))M'Cl] with T1PF(6) leads to the formation of cationic derivatives [(dppe)M(mu-2-C6F4PPh2)(2)M']PF6 with P-M'-P (6PtAu) or P-M'-C (7PdAu, 7PtAu) bonding situations around the coinage metal.