The action of PhI . Cl-2 on W2Cl4(PMe(3))(4) in 1:1 mole ratio gives brown 1,3,6-W2Cl5(PMe(3))(3). The EPR at 10 K in frozen CH2Cl2 solution has a broad signal at g 1.83. The molecular structure was determined by X-ray crystallography and shows a W-W distance of 2.291(1) Angstrom, about 0.03 Angstrom longer than that in W2Cl4(PMe(3))(4). Crystal data : monoclinic space group C2/c with cell dimensions of a 13.423(2) Angstrom, b = 12.0768(9) Angstrom, c 28.247(5) Angstrom, beta = 93.360(7)degrees, V = 457,1(1) Angstrom(3), and Z = 8. There is a 1.8% orientational disorder. When a solution of W2Cl6(PMe(3))4 in CH2Cl2 plus hexanes was allowed to stand at -15 degrees C for several months, brown crystals of [HPMe(3)](2)[W2Cl8(PMe(3))]. CH2Cl2 were obtained. The anion is a face-sharing bioctahedron, with a W-W bond length of 2.433(1) Angstrom. Crystal data : monoclinic space group P2(1)/m with cell dimensions of a 9.398(1) Angstrom, b = 9.836(2) Angstrom, c 16.687(5) Angstrom, beta = 97.78(2)degrees, V = 1528.4(6) Angstrom(3), and Z = 2.