Synthesis and Structure of Multinuclear Pd(II) Complexes Bridged by Phosphide or Azide Ligands

The synthesis and structure of phosphide- and azide-bridged multinuclear Pd(II) complexes bearing phosphine ligands [PdX(μ-X')(PR₃)] (X = Cl and N₃; X' = PR₂ ^' and N₃; n = 2 and 4) are reported. The oxidative addition of R₂ ^'PCl to Pd(PMe₃)₂ furnished the phosphide-bridged dinuclear Pd(II) complexes [PdCl(μ-PR₂ ^')(PMe₃)]₂ [R' = Pr (1a) and Cy (1b)]. However, the oxidative addition of (o-tolyl)₂PCl to Pd(PMe₃)₂ produced a nonbridged mononuclear Pd(II) complex with the bis(o-tolyl)phosphinic ligand, trans-[Pd(PMe₃)₂{P(O)(o-tolyl)₂}] (2), via oxidation of the phosphinyl ligand. The reaction of the chloride-bridged dinuclear Pd(II) complexes [PdCl(μ-Cl)(PR₃)]₂ [PR₃ = PEt₃ (3a) and PPhMe₂ (3b)] with NaN₃ afforded the azide-bridged dinuclear and tetranuclear Pd(II) complexes [Pd(N₃)(μ-N₃)(PEt₃)]₂ (4) and [Pd(N₃)(μ-N₃)(PPhMe₂)]₄ (5). Comparisons of the X-ray structures of 4 and 5 show that the square-planar molecular geometry of the Pd(II) centers of 4 are more distorted than those of 5. Density functional theory calculations suggest that the tetranuclear eight-membered ring structure like 5 is more stable than the dinuclear four-membered ring structure like 4 in the gas phase in both PEt₃ and PPhMe₂ systems. However, because the relative energy difference between the four-membered and eight-membered ring structures is small in the PEt₃ system with smaller steric hindrance compared with PPhMe₂, it is assumed that this difference is compensated by the crystal packing energy, and the dinuclear four-membered ring complex 4 is actually obtained.