One pot synthesis of dimanganese carbonyl complexes containing sulfur and phosphorus donor ligands using tricarbonylpentadienylmanganese

The reaction of tricarbonylpentadienylmanganese with aryl mercaptans in the presence of phosphines or phosphites afforded dinuclear complexes, [Mn2(CO)4(μ-CO)(μ-SR)2(PR′3)2]; R = Ph for PR′3 = PPh3, PMe3, P(OMe)3, P(OEt)3, PMePh2 and R = m-, p-NH2C6H4S–, for PR′3 = PPh3 in one pot synthesis. Two reaction routes were proposed for the formation of the dinuclear complexes depending on the relative basicity of the sulfur vs. phosphine ligands. Characterization of the complexes was effected in solution and, for [Mn2(CO)4(μ-CO)(μ-SPh)2(PPh3)2], [Mn2(CO)4(μ-CO)(μ-SPh)2(P(OEt)3)2], and [Mn2(CO)4(μ-CO)(μ-SPh)2(PMe3)2], by X-ray crystallographic analysis.

Graphical abstractThe reaction of tricarbonylpentadienylmanganese with aryl mercaptans in the presence of phosphines or phosphites afforded dinuclear complexes [Mn2(CO)4(μ-CO)(μ-SR)2(PR′3)2]; R = Ph for PR′3 = PPh3, PMe3, P(OMe)3, P(OEt)3, PMePh2 and R = m-, p-NH2C6H4S–, for PR′3 = PPh3 in one pot synthesis. Two reaction routes were proposed for the formation of the dinuclear complexes depending on the relative basicity of the sulfur vs. phosphine ligands. Characterization of the complexes was effected in solution and, for [Mn2(CO)4(μ-CO)(μ-SPh)2(PPh3)2] and [Mn2(CO)4(μ-CO)(μ-SPh)2(PMe3)2], by X-ray crystallographic analysis.Figure optionsDownload full-size imageDownload as PowerPoint slide