Behavior of P−Pt and P−Pd Bonds in Phosphido Complexes toward Electrophilic Fragments

The reactions between the unsaturated 30-valence-electron-count [(C6F5)2Pt(μ-PPh2)2M(PPh3)] (M = Pt, Pd) and [M′(OClO3)PPh3] (M′ = Ag, Au) yield the cationic trinuclear [(C6F5)2Pt(μ-PPh2)2M(PPh3)(M′PPh3)][ClO4] (M = Pt, Pd; M′ = Ag, Au), which displays Pt−M and M−M′ bonds. The X-ray structures of the complexes reveal that the core of the molecules is planar and the Pt−M and M−M′ distances point to the presence of Pt−M and M−M′ bonds. A computational study on the formation of these complexes and the analysis of the interaction between the binuclear fragment [(C6F5)2Pt(μ-PPh2)2Pt(PPh3)] and the cation [Ag PPh3]+ has been carried out on the basis of density functional theory and shows that the Ag center interacts weakly with M and P (PPh2 ligand) atoms of the binuclear fragment.