text: The electronic structures of Fe(SCNMe)(NE), where E=O, S, or Se were calculated using Density Functional Theory methods. It was found that the large Mulliken spin density remained concentrated on the Fe(NE) core and Fe-N distances experienced little change from the chalcogen atom used. The HOMO of both nitrosyl and thionitrosyl complexes retained 1a (d) character. The small changes in the energies of the spin orbitals of the complexes, particularly the decreased energetic gap between 2b and 1b and 2b and 1b orbitals is attributed to NS being a weaker π-acceptor than NO.