The heats of formation of saturated and unsaturated diaminocarbenes (imadazol(in)-2-ylidenes) have been calculated by using high levels of ab initio electronic structure theory. The calculations were done at the coupled cluster level through noniterative triple excitations with augmented correlation consistent basis sets up through quadruple. In addition, four other corrections were applied to the frozen core atomization energies: (1) a zero point vibrational correction; (2) a core/valence correlation correction; (3) a scalar relativistic correction; (4) a first-order atomic spin-orbit correction. The value of Delta H-f(298) for the unsaturated carbene 1 is calculated to be 56.4 kcal/mol. The value of Delta H-f(298) for the unsaturated triplet carbene (3)1 is calculated to be 142.8 kcal/mol, giving a singlet-triplet splitting of 86.4 kcal/mol. Addition of a proton to 1 forms 3 with Delta H-f(298) (3) = 171.6 kcal/mol with a proton affinity for 1 of 250.5 kcal/mol at 298 K. Addition of a hydrogen atom to 1 forms 4 with Delta H-f(298)(4) = 72.7 kcal/mol and a C-H bond energy of 35.8 kcal/mol at 298 K. Addition of H- to 1 gives 5 with Delta H-f(298)(5) = 81.2 kcal/mol and 5 is not stable with respect to loss of an electron to form 4. Addition of H-2 to the carbene center forms 6 with Delta H-f 298(6) = 41.5 kcal/mol and a heat of hydrogenation at 298 K of -14.9 kcal/mol. The value of Delta Hf 298 Z for the saturated carbene 7 (obtained by adding H-2 to the C=C bond of 1) is 47.4 kcal/mol. Hydrogenation of 7 to form the fully saturated imidazolidine, 8, gives Delta H-f(298)(8) = 14.8 kcal/mol and a heat of hydrogenation at 298 K of -32.6 kcal/mol. The estimated error bars for the calculated heats of formation are +/- 1.0 kcal/mol.