Structural Characterization of a Fluorido-Amide of Niobium, and Facile CO2 Incorporation Affording a Fluorido-Carbamate

We have prepared the first niobium(V) compounds bearing fluorido and monodentate amido ligands (1a–c), which are tetranuclear cations, by the reaction between NbF5 and Me3SiNMe2 in the presence of a chloride (or bromide) source. The fluorido/carbamato derivative NbF2(O2CNMe2)3 (2) was obtained in good yield from the reaction of NbF5 and Me3SiNMe2 in the presence of carbon dioxide at 1 atm pressure and ambient temperature. All the products were characterized by analytical and spectroscopic (IR, multinuclear NMR) methods, and by X‐ray diffraction in the cases of 1b,c. DFT calculations were useful for elucidating the structures of the products and also for providing an insight into the reaction pathways.