The following, previously known, multiply bonded dirhenium and ditungsten compounds have been characterized by X-ray crystallography: Re2C14(PMe3)4 (l), [RezC14(PMe3)4]Re04 (2), RezC14(P-n-Pr3)4 (3), Re2Br4(P-n-Pr3)4 (4), and W,CI,(P-n-B u~)~C~H~ (5). Pertinent crystal data are as follows: for 1, monoclinic space group C2/c, a = 18.058 (3) A, 6 = 9.247 (1) A, c = 18.725 (2) A, 0 = 124.64 (I)', V = 2572 (1) A3, Z = 4; for 2, orthorhombic space group Pmcn, a = 14.166 (2) A, b = 9.799 (2) A, c = 20.836 (4) A, V = 2892 (I) A', 2 = 4; for 3, monoclinic space group 12/a, a = 18.564 (6) A, 6 = 14.766 (6) A, c = 19.283 (5) A, 6 = 106.21 (2)'. V = 5076 (3) A3, Z = 4; for 4, monoclinic space group C2/c, a = 18.513 (5) A, 6 = 14.767 (4) A, c = 19.381 (6) A, p = 104.57 ( 2 ) O , V = 5128 (2) A', 2 = 4; for 5, triclinic space grou Pi, a = 13.947 ( I ) A, b = 20.743 (7) A, c = 13.612 (6) A, a = 96.28 (3)O, 6 = 117.78 ( 2 ) O , y = 74.73 (2)", V = 3361 (2) i3, 2 = 2. Complexes 3-5 exhibitan unprecedented form of crystallographic disorder for this type of compound in which the dimetal unit adopts three orientations within a quasi-cube of halide and phosphine ligands. These complexes have the dimetal unit in three orientations with occupancies of 43%. 29%. 28% for 3, 50%, 32%, 18% for 4, and 88%, 8.5%, 3.5% for 5. Compounds 1 and 2 are not disordered in any way.The role played by the size and shape of the phosphine in promoting this type of disorder is discussed.