The stability of the experimentally known complex (Et3P)2Ir(CO)(Cl)(F)(SF3) of the third row transition metal iridium suggests that SF3 complexes of the third row transition metals might be viable species in contrast to the SF3 complexes of the first row transition metals previously studied by theoretical methods. However, the metal complexes [M](SF3) ([M] = Ta(CO)5, Re(CO)4, CpW(CO)2, CpOs(CO), and CpPt) containing three-electron donor tetrahedral SF3 ligands are thermodynamically disfavored relative to the isomeric [M](SF2)(F) derivatives with predicted energy differences ranging from -19 to -44 kcal/mol. The one exception is an Ir(SF3)(CO)3 isomer containing a one-electron donor pseudo-square-pyramidal SF3 ligand having essentially the same energy as the lowest energy Ir(SF2)(F)(CO)3 isomer. This, as well as the stability of the known (Et3P)2Ir(CO)(Cl)(F)(SF3), suggests that metal complexes containing one-electron donor pseudo-square-pyramidal SF3 ligands might be viable synthetic objectives in contrast to those containing three-electron donor tetrahedral SF3 ligands. The [M](SF2)(F) derivatives formed by sulfur-to-metal fluorine migration from isomeric [M](SF3) complexes are predicted to be viable toward SF2 dissociation to give the corresponding [M](F) derivatives. This suggests the possibility of synthesizing metal complexes of the difluorosulfane (SF2) ligand via the corresponding metal trifluorosulfane complexes with the SF3(+) cation as the ultimate source of the SF2 ligand. Such a synthetic approach bypasses the need for the very unstable SF2 as a synthetic reagent.