Anionic tetranuclear complexes with the molecular formula [NBu4](2)[Pd-4(mu-PPh2)(2)(mu-X)(4)(C6F5)(4)][X = Cl (1), Br (2)1 were obtained by reaction of [NBu4](2)[Pd-2(mu-PPh2)(2)(C6F5)(4)] and PdCl2 (or K-2[PdCl4]) in acetone, followed by reaction with KBr for 2. The reactions of 1 with neutral monodentate (L) or bidentate (L-L) ligands afford the dinuclear derivatives [Pd-2(mu-PPh2)(mu-Cl)(C6F5)(2)L-2] [L= PPh3 (3), py (4)] or [Pd-2(mu-PPh2)(C6F5)(2)(L-L)(2)](n) [n = I -, L-E = acac (6); n = If, L-E = bipy (7) or phen (8)]. The structures of complexes H and 7 were determined by single-crystal X-ray diffraction studies 1 The bis(acetone) solvate of complex 1, [NBu4](2)[Pd-4(mu-PPh2)(2)(mu-Cl)(4)- Angstrom, c = 23.868(8) Angstrom, beta = 101.10(3)degrees, V = 4527.6(15) Angstrom(3), and Z = 2. The central core of the anion has the shape of a rectangle with the four Pd atoms in the corners. The hexane solvate of complex 7, [Pd-2(mu-PPh2)(C6F5)(2)-bipy)(2)][ClO4].C6H14, crystallizes in the monoclinic system, space group P2(1)/n, with a 16.214(3) Angstrom, b = 10.311-(2) Angstrom, c = 28.380(6) Angstrom, beta = 100.82(3)degrees, V = 4660(2) Angstrom(3), and Z = 4. In both complexes, the long Pd ... Pd distances (> 3.1 Angstrom) clearly point to the absence of any Pd-Pd interaction.