The direct oxidation of Mo 2 (DTolF) 4 with PhICl 2 in CH 2Cl 2 and crystallization from toluene resulted in the isolation of the edge-sharing dimolybdenum (III,IV) compound Mo 2 (DTolF) 4Cl 3·C 7H 8·C 6H 14 ( 1), containing two DTolF − ligands that are bridging, one that is chelating and one that bridges the metal centers in a monodentate fashion. The oxidation of Cr 2 (DTolF) 4 by the same method yielded the symmetrical dichromium(III,III) compound Cr 2(DTolF) 4Cl 2·3C 6H 6 ( 2), containing two bridging and two chelating DTolF − ligands. Refluxing MoCl 3(THF) 3 and HDPhF with PPh 4Cl in o-dichlorobenzene followed by crystallization from CH 2Cl 2 yielded [PPh 4][Mo 2(DPhF) 2(NPh)Cl 5]·2CH 2Cl 2 ( 3), in which the bridging imido NPh 2− group is thought to have resulted from the cleavage of formamidine molecules. The structures of these compounds have been determined by X-ray crystallography and their crystallographic data are as follows: 1, monoclinic P2 1/ n with a = 14.384(2), b = 20.913(2), c = 23.601(1) A ̊ , β = 102.498(6)°, V = 6931(1) A ̊ 3, Z = 4, R = 0.049, wR2 = 0.121 ; 2,triclinic P 1 with a = 10.128(4), b = 11.817(4), c = 14.859(7) A ̊ , α = 103.51(4), β = 95.80(4), γ = 95.80°, V = 1707(1) A ̊ 3, Z = 1, R = 0.067, R w = 0.084 ; 3, triclinic P 1 with a = 15.268(8), b = 20.024(2), c = 10.401(1) A ̊ , α = 90.36(1), β = 97.80(2), γ = 69.92(2)°, V = 2956(2) A ̊ 3, Z = 2, R = 0.043, wR2 = 0.105 .