Treatment of the complex [W(CO)(5) [PPh2(CS2Me)]] (2) with [Pd(PPh3)(4)] (1) affords binuclear complexes such as anti-[(Ph3P)(2)Pd(mu-eta(1),eta(2)-(CS2Me)PPh2]W(CO)(5)] (3), syn-[(Ph3P)(2)Pd[mu-eta(1),eta(2)-(CS2Me)PPh2]W(CO)(5)] (4), and trans-[W(CO)(4)(PPh3)(2)] (5) In 3 and 4, respectively, the W and Pd atoms are in anti and syn configurations with respect to the P-CS2 bond of the diphenyl(dithiomethoxycarbonyl)phosphine ligand, PPh2(CS2Me). Complex 3 undergoes extensive rearrangement in CHCl3 at room temperature by transfer of a PPh3 ligand from Pd to W, eliminating [W(CO)(5)(PPh3)] (7), while the PPh2CS2Me ligand transfers from W to Pd to give [[(Ph3P)Pd[mu-eta(1),eta(2)-(CS2Me)PPh2]](2)] (6). In complex 6, the [Pd(PPh3)] fragments are held together by two bridging PPh2(CS2Me) ligands. Each PPh2(CS2Me) ligand is pi-bonded to one Pd atom through the C=S linkage and sigma-bonded to the other Pd through the phosphorus atom, resulting in a six-membered ring. Treatment of Pd(PPh3)(4) with [W(CO)(5)[PPh2[CS2(CH2)(n)CN]]] (n = 1, 8a; n = 2, 8b) in CH2Cl2 affords syn-[(Ph3P)(2)Pd[mu-eta(1),eta(2)-[CS2(CH2)(n)CN] (CO)(5)] (n = 1, 9a; n = 2, 9b). Similar configurational products syn-[(Ph3P)(2)Pd[mu-eta(1),eta(2)-(CS2R)PPh2]W(CO)(5)] (R = C2H5, C3H5, C2H4OH, C3H6CN, 11a-d) are synthesized by the reaction of Pd(PPh3)(4) with [W(CO)(5)[PPh2(CS2R)]] (R = C2H5, C3H5, C2H4OH, C3H6CN, 10a-d). Although complexes 11a-d have the same configuration as 9a,b, the SR group is oriented away from Pd in the former and near Pd in the latter. In these complexes, the diphenyl(dithioalkoxycarbonyl)phosphine ligand is bound to the two metals through the C=S pi-bonding and to phosphorus through the a-bonding. All of the complexes are identified by spectroscopic methods, and the structures of complexes 3, 6, 9a, and lid are determined by single-crystal X-ray diffraction. Complexes 3, 9, and lid crystallize in the triclinic space group P (1) over bar with Z = 2, whereas 6 belongs to the monoclinic space group P2/c with Z = 4. The cell dimensions are as follows: for 3, a = 10.920(3) Angstrom, b = 14.707(5) Angstrom, c = 16.654(5) Angstrom, alpha = 99.98(3)degrees, beta = 93.75(3)degrees, gamma = 99.44(3)degrees; for 6, a = 15.106(3) Angstrom, b = 9.848(3) Angstrom, c = 20.528(4) Angstrom, beta = 104.85(2)degrees; for 9a, a = 11.125(3) Angstrom, b = 14.089(4) Angstrom, c = 17.947(7) Angstrom, alpha = 80.13(3)degrees, beta = 80.39(3)degrees, gamma = 89.76(2)degrees; for 11d, a = 11.692(3) Angstrom, b = 13.602(9) Angstrom, c = 18.471(10) Angstrom, alpha = 81.29(5)degrees, beta = 80.88(3)degrees, gamma = 88.82(1)degrees.