The linear trinuclear iron complex Fe 3 (SPh) 6 (CO) 6 with bridging benzenethiolate ligands is the subject of temperature-and field-dependent Mössbauer studies and of temperature-dependent magnetic susceptibility studies. The results reveal the two terminal iron atoms to be diamagnetic Fe(II) and the central iron atom to be high-spin Fe(II). The latter exhibits an enhanced effective magnetic moment compared to the ( S = 2) spin-only value of 4.9 μ B, and its magnetic Mössbauer pattern is dominated by a positive (!) internal field. Complementary to the experimental studies also theoretical studies are performed. Local density molecular orbital and ligand-field calculations yield an orbitally degenerate ground state that accounts for the unusual electronic and spectroscopic properties. With these results inconsistencies in previously reported spectroscopic studies of Fe 3 (SPh) 6 (CO) 6 are resolved.