The dicarbonyl complex trans-[W2Cp2(mu-PPh2)(2)(CO)(2)] (Cp = eta(5)-C5H5) reacted rapidly with NO (5% in N-2) at 273 K to give selectively cis-[W2Cp2(mu-PPh2)(2)(NO)(2)]. In contrast, the analogous reactions of monocarbonyl [W2Cp2(mu-PPh2)(2)(mu-CO)] yielded either trans-[W2Cp2(mu-PPh2)(2)(NO)(2)] or the nitrito complex [W2Cp2(mu-PPh2)(2)(ONO)(CO)(NO)] (W-W = 2.9797(4) angstrom), depending on experimental conditions, with the latter presumably arising from reaction with trace amounts of oxygen in the medium. The stereoselectivity of the above reactions can be rationalized by assuming the participation of 33-electron [W2Cp2(mu-PPh2)(2)(CO)(NO)] intermediates which rapidly add a second molecule of NO via eta(2)-C5H5 intermediates to eventually yield the corresponding dinitrosyls with inversion of the stereochemistry at the dimetal center, as supported by density functional theory (DFT) calculations. The nitrito complex was thermally unstable and evolved through oxygen transfer either to the carbonyl ligand, to yield the above dinitrosyls with release of CO2, or to the phosphide ligand, to give the phosphinito derivative cis-[W2Cp2(mu-OPPh2)(mu-PPh2)(NO)(2)], depending on experimental conditions. According to DFT calculations, the first process would involve transient dissociation/recombination of the nitrite ligand followed by coupling to carbonyl to give an intermediate with a chelate W{C,N-C(O)ON(O)} ring. Indeed, the nitrite ligand could be easily removed upon reaction of the nitrito complex with Na(BAr'(4)), but immediate decomposition also took place to render the electron-precise dicarbonyl [W2Cp2(mu-PPh2)(2)(CO)(2)(NO)]BAr'(4) (W-W = 2.9663(3) angstrom) as the unique product (Ar' = 3,5-C6H3(CF3)(2)). Attempts to decarbonylate the latter complex photochemically yielded instead the oxo derivatives cis- and trans-[W2Cp2(mu-PPh2)(2)(O)(NO)]BAr'(4) as the only isolable products (W-W = 2.980(2) and 3.0077(3) angstrom, respectively).