Anion photoelectron spectra and density functional calculations are reported for NbCr(CO)$_{2}^{-}$ and NbCr(CO)$_{3}^{-}$ complexes prepared by addition of Cr(CO)$_{6}$ vapor to a flow tube equipped with a niobium cathode discharge source. Electron affinities ($pm$ 0.007 eV) are measured to be 1.668 eV for NbCr(CO)$_{2}$ and 1.162 eV for NbCr(CO)$_{3}$, values which exceed the 0.793 eV electron affinity previously measured for ligand-free NbCr. The vibrationally-resolved 488 nm photoelectron spectra are compared with Franck-Condon spectra predicted for various possible isomers and spin states of the anionic and neutral metal carbonyl complexes. Results are also compared with photoelectron spectra of the corresponding chromium carbonyl complexes and of NbCr and NbCr$^{-}$, which have formal bond orders of 5.5 ($^{2}Delta$) and 6 ($^{1}Sigma^{+}$), respectively. These comparisons help to elucidate the effects of sequential carbonylation on this multiple metal-metal bond, and of the formation of this bond on the chromium-carbonyl interactions.
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