The reaction of elemental sulfur with the cis-divacant octahedral complex [(pyrr(2)py)Fe(OEt2)] (1; PYrr(2)Py(2-) = 3,5-'Bu-2-bis(pyrrolyl)pyridine) yields the iron dimer [(pyrr-1-S-PyrrPy)Fe](2) (2; pyrr-1-S-pyrrPy(2-) = 3,5-(Bu-t(2)-pyrrolyl) (1-S-3,5-Bu-t(2)-pyrrol)pyridine) resulting from a pyrr(2)py(2-) ligand based S-oxidation of one pyrrole arm. Addition of the phosphorus ylide H2CPPh3 to 1 forms the ylide adduct [(pyrr(2)py)Fe-(CH2PPh3)] (3), which upon reaction with elemental sulfur produces a rare example of a sulfurmethylenephosphorane adduct, [(pyrr(2)py)Fe(SCH2PPh3)] (4). The sulfur-oxidized pyrrole group of the ligand pyrr-1-S-pyrrpy(2-) can be reversed, since complex 2 exhibits S atom transferability via the addition of 2 equiv of H2CPPh3 to yield a mixture of compounds 3 and 4. For all complexes reported, the ferrous ion remains S = 2. Complexes 2-4 were characterized by single-crystal X-ray diffraction as well as H-1 NMR spectroscopy, solid and solution magnetic studies, and Fe-57 Mossbauer spectroscopic measurements.