We have re-examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] (1, Cp = η5-cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligand to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li (3) that is stable only below –40 °C. Full characterization of 3 (including single crystal X-ray diffraction) was performed. This complex decomposes quickly above –20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li (2). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so-far unique behavior of the N2 ligand in 1. DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal-coordinated N2 remains to be demonstrated.