Complex [Mo2Cp2(mu-PCy2)(mu-NO)-(NO)(2)] (1) was prepared by reacting [Mo2Cp2(mu-H)(mu-PCy2)(CO)(4)] with 2 equiv of [NO]BF4 and then treating the resulting product [Mo2Cp2(mu-PCy2)(CO)(2)(NO)(2)](BF4) with NaNO2 at 323 K, and it was shown to display a bridging nitrosyl ligand with significant pyramidalization at the N atom, a circumstance related to an unusual behavior concerning degradation of the bridging nitrosyl. Indeed, complex 1 reacts with HBF4 center dot OEt2 to give the nitroxyl-bridged derivative [Mo2Cp2(mu-PCy2)(mu-kappa(1):eta 2-HNO)(NO)(2)](BF4), is reduced by Zn(Hg) in the presence of trace H2O to give the amido complex [Mo2Cp2(mu-PCy2)(mu-NH2)(NC))(2)], and reacts with excess P(OPh)(3) to give the phosphoraniminato-bridged derivative [Mo2Cp2(mu-PCy2){mu-NP(OPh)(3)}(NO)(2)].