Reaction of 1,4-diisocyanobenzene or 4-isocyanobenzonitrile with trans-W(N-2)(2)(DPPE)(2) (DPPE 1,2-bis(diphenylphosphino)ethane) produced cis-WL(2)(DPPE)(2), where L = 1,4-diisocyanobenzene or 4-isocyanobenzonitrile. cis-(CNC6H4NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P (1) over bar, with a = 12.848(3) Angstrom, b = 13.596(3) Angstrom, c = 19.072(3) Angstrom, alpha = 78.99(2)degrees, beta = 70.66(2)degrees, gamma = 65.26(2)degrees, V = 2849.8(11) Angstrom(3), and Z = 2. cis-(NCC6H4NC)(2)W(DPPE)(2) crystallizes in the triclinic space group P (1) over bar, with a = 12.712(3) Angstrom, b = 13:700(3) Angstrom, c = 19.109(3) Angstrom, alpha = 77.91(2)degrees, beta = 70.63(2)degrees, gamma = 64.75(2)degrees, V = 2830.7(13) Angstrom(3), and Z = 2. Both compounds possess a distorted octahedral geometry about the metal center, with the two isocyanide ligands cis to one another. The isocyanide ligands are substantially bent along the CNC axis of the isocyanide group coordinated to tungsten. For the complex containing the symmetric ligand, CNC6H4NC, the mean CNC angle for the coordinated end of the isocyanide is 139.1(11)degrees, the average W-C bond length is 1.86(1) Angstrom, and the C=N bond lengths have a mean value of 1.30(2) Angstrom. These data indicate substantial back-donation from an electron-saturated tungsten atom. This is supported spectroscopically, with substantial shifts to lower wavenumbers for the C-N stretching frequencies of the coordinated isocyanide groups. Similar trends are observed in cis-(NCC6H4NC)(2)W(DPPE)(2). Both compounds contain electron-rich metals surrounded by large ligands which apparently protect the metals from atmospheric oxidation. The isocyanide ligands in both complexes contain a second coordinating group pointing away from the metal into the environment surrounding the molecules, providing the potential for polymetallic complexes containing metals in a variety of oxidation states.