Two compounds containing the cations Mo-2(DPhIP)(4)(n+), n = 1 or 2 and DPhIP = the anion of 2,6-diphenyliminopiperidine, have been obtained by oxidation of the quadruply-bonded Mo-2(DPhIP)(4) species. The first oxidation process conserves the structure but results in a slight increase of the Mo-Mo distance from 2.114(1) to 2.136(2) Angstrom in [Mo-2(DPhIP)(4)](PF6). 2CH(2)Cl(2) (1.2CH(2)Cl(2)). However, the second oxidation process breaks the dimolybdenum bond, giving a bioctahedral complex, [Mo-2(DPhIP)(4)](BF4)(2). 5CH(3)CN . Et2O (2.5CH(3)CN . Et2O), with Mo Mo separation of 2.9954(7) Angstrom. Crystallographic data for 1.2CH(2)Cl(2) are space group C2/c, a = 17.1891(9) Angstrom, b = 17.807(1) Angstrom, c = 24.210(2) Angstrom, beta = 106.403(4)degrees, Z = 4; for 2.5CH(3)CN . Et2O, space group P2(1)/n, a = 16.523(5) Angstrom, b = 27.418(5) Angstrom, c = 18.163(3) Angstrom, beta = 93.48(2)degrees, Z = 4.