The effect of substituents at the heteroatom on the electronic structures of different N-heterocyclic carbenes (1, 2 and 3), silylene (4) and germylene (5) are examined using Density Functional Theory. The kinetic and thermodynamic stabilities of these molecules are assessed by examining the HOMO-LUMO gap and hydrogenation energies, respectively. The extent of cyclic electron delocalization present in these five-membered ring systems are quantified with the help of NICS calculations. The ligating properties of 1-5 and the recently synthesized free abnormal carbene 6 (Bertrand et al., Science, 2009, 326, 556-559) are examined by looking at the energies of the sigma symmetric electron-donating orbital of the respective molecules. Among the systems considered, 6 is found to have the strongest sigma-donating ability. A comparative study of the ligating properties between the two isomeric carbenes 1 and 6 is performed by calculating the carbonyl stretching frequencies of some iridium carbonyl complexes of these two tautomeric carbenes.