To shed light on the bonding situation in the keteniminyl anions we carried out DFT calculations at the BP86+D3(BJ)/def2-TZVPP level of theory. We analyzed the naked anions [Ph2OPC-L2] -with L2 = CNAr (3b) as an example of an electron-poor and L2 = CNCy (3d) for an electron-rich keteniminyl anion and compared their structures to the protonated congeners, with the proton being bound either to the C1 carbon atom (ketenimine, 3-HC) or the nitrogen atom (ynamine 3-HN). The calculated Mayer bond orders (MBO) suggest an intermediate bonding situation in the keteniminyl anions (Figure ). The MBOs of the newly formed C-C and C-N bond confirm the multiple bond character of both bonds in 3b and 3d. These bond orders fall between those calculated for the protonated congeners, the ketenimine and ynamine. For instance, the C-C bond order for 3b amounts to 2.20, while the double bond in ketenimine 3b-HC has a value of 1.71 and the triple bond in the ynamine 3b-HN a value of 2.52. The C-C bond order is higher in the phenyl derivative 3b (2.20) than in the cyclohexyl system 3d (1.85), which correlates with the increased ynamide character 3' of electron-poor keteniminyl anions as indicated by the spectroscopic and crystallographic studies. This trend is further evidenced by the significant reduction in the calculated bending angle at C1 (P1-C1-C2) from 3b to 3d as well as the shape of the highest occupied molecular orbital (HOMO), which is delocalized across the C-C-N linkage and the entire aryl substituent in 3b, while it is mostly localized at the C1 carbon and nitrogen atom in 3d.