Tetrapalladium complex with bridging germylene ligands. Structural change of the planar Pd4Ge3 core

Article abstract of DOI:10.1021/ja208565q

A complex with a planar hexagonal Pd₄Ge₃ core, [Pd{Pd(dmpe)}₃(μ ₃-GePh₂)₃], was synthesized and characterized by X-ray and NMR measurements as well as by DFT calculations. 4-tert-Butylbenzenethiol converted the Pd₄ complex into ahexapalladium complex, [{Pd₃(μ-GePh₂)_2- (μ-H)(μ₃-GePh₂(SC₆H₄ ^tBu-4))}₂(μ-dmpe)], composed of two Pd ₃Ge₃ units bridged by a dmpe ligand. The addition of CuI or AgI to the Pd₄ complex yielded [Pd(μ-MI){Pd-(dmpe)} ₃(μ₃-GePh₂)₃] (M = Cu, Ag), in which Cu or Ag bridges a Pd-Pdbond of the Pd₄Ge₃ core. The CuI adducts in solution undergo a pivot motion of the CuI on the surface of the Pd₄Ge₃ plane on the NMR time scale.