Bond Cleavage Of Ligand Research Articles

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)

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.

Iron carbonyl complexes from 2-[2,3-diaza-4-(2-thienyl)buta-1,3-dienyl]thiophene: NN bond cleavage and cyclometalation

When thienyl Schiff base 1, derived from 2-formylthiophene and hydrazine, reacted with Fe 2(CO) 9 in n-hexane, three major complexes were obtained: (1) a diironhexacarbonyl complex with two 2-thienylmethylideneamido bridging ligands 2, which resulted from the NN bond cleavage of ligand 1; (2) a doubly cyclometalated di-μ-di-(η 1:η 2-thienyl; η 1:η 1( N))bis(hexacarbonyldiiron) complex ( 3); and (3) a cyclometalated (μ-η 1:η 2-thienyl; η 1:η 1( N))hexacarbonyldiiron complex ( 4). Molecular structures of compounds 1a, 1c, and 2a have been determined by single-crystal X-ray diffraction.