A complex with a planar hexagonal Pd4Ge3 core, [Pd{Pd(dmpe)}(3)(mu(3)-GePh2)(3)], was synthesized and characterized by X-ray and NMR measurements as well as by DFT calculations. 4-tert-Butylbenzenethiol converted the Pd-4 complex into a hexapalladium complex, [{Pd-3(mu-GePh2)(2)-(mu-H)(mu(3)-GePh2((SC6H4Bu)-Bu-t-4))}(2)(mu-dmpe)], composed of two Pd3Ge3 units bridged by a dmpe ligand. The addition of CuI or AgI to the Pd-4 complex yielded [Pd(mu-MI){Pd-(dmpe)}(3)(mu(3)-GePh2)(3)] (M = Cu, Ag), in which Cu or Ag bridges a Pd-Pd bond 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