Kinetic stabilization using bulky m-terphenyl substituents is the key to the isolation of the diarylantimony and diarylbismuth phosphaethynolates (2,6-Mes2C6H3)2EPCO and the related N-heterocyclic carbene complexes (2,6-Mes2C6H3)2EP(O)C(IMe4) (E=Sb, Bi; IMe4=1,3,4,5-tetramethylimidazol-2-ylidene), which have been fully characterized crystallographically and spectroscopically. The experimental characterization was augmented by a DFT based real space bond indicator analysis of the electron density, including AIM, NCI, and ELI-D methods.