Since the detection of the first interstellar molecules, the question arose as to how small molecules evolve into complex organic molecules and prebiotic systems. Many theories and concepts have been formulated to explain and understand how chemical diversity and complexity increased through the reaction of small molecules in the interstellar medium (ISM). To date, more than 300 molecules ranging from small to large (carbon chains, fullerenes) molecules as well as radicals and ions have been observed in the ISM. Some of these molecules, like CO, CO2 or NH3, are stable terrestrial compounds, while others are highly reactive and transient species. Reconstructing the path of chemical evolution is challenging and requires multi-disciplinary approaches combining astronomical observations with computational modeling and laboratory experiments. Often, a bottom-up approach is used to investigate the increase of molecular complexity by analyzing the reactivity of reactive species with other (interstellar) molecules. These studies usually rely on matrix isolation or mass spectrometry experiments to synthesize these transient species and to simulate the conditions in space. The handling of such small molecules, radicals and ions is usually difficult, if not impossible, in bulk solutions due to their notorious reactivity, which often results in uncontrolled follow up reactions. Small nitrogen and oxygen containing carbon compounds are of particular interest for the evolution or prebiotic systems since they are assumed to be precursors to the molecules of life such as amino acids or nucleobases. One of these molecules is cyanoketene (1), which may add water to form β-amino acids. While several N-and O-containing organic molecules have been observed in the ISM (Fig. ), cyanoketene (1) has not been detected until to date, but has been subject of numerous early matrix isolation, gas phase and computational studies, addressing possible isomers and routes for its formation. The cyanoketene anion, [NCCCO] -(2), has likewise been proposed to be an interstellar species, 20 but unlike its isoelectronic analogue, carbon suboxide (C3O2), not been isolated, but only been prepared in gas phase and detected by mass spectrometry experiments. Besides being a promising precursor to complex organic molecules, the cyanoketene anion also represents a fundamentally interesting molecule to understand chemical bonding and challenge existing bonding concepts. Due to its assumed cumulene-like structure it can be described by the different resonance forms 2c and 2d (Figure ). However, also the bent structural isomer 2a is conceivable which may also be regarded as a coordination complex of carbon (2d) with a carbon monoxide and cyanido ligand, both of which are frequently used ligands in transition metal complexes.