Cleavage of phosphorus-sulfur bond and formation of (μ4-S)Fe4 core from photochemical reactions of Fe(CO)5 with [(RO)2PS2]2; (R = Me, Et, iPr)

Abstract

When hexane or alcohol solutions containing iron pentacarbonyl and bis(dialkoxythiophosphoryl) disulfide (R = Me (1), Et (2), or Pri (3)), were irradiated with 366 nm light, under argon atmosphere at 0 °C, clusters [(μ-RS)Fe2(CO)6](μ4-S)[(μ-(OR)2P)Fe2(CO)6] (4: R = Me, 5: R = Et) and [Fe2(CO)6S{P(OiPr)2}]2 (6) were obtained in hexane and [Fe4(CO)8(μ-CO)2(μ4-S)2P(OR)3] (7: R = Me, 8: R = Et) in MeOH and EtOH respectively. These reactions involve P–S bond cleavage of ligands and desulfurization process and Fe-S and Fe-P bond formation. Computational and experimental bond parameters have been studied on the new compounds.