Oxygen Atom Transfer Reactions from Dioxygen to Phosphines via a Bridging Sulfur Dioxide in a Trinuclear Cluster Complex of Rhenium, [(Ph₃P)₂N][Re₃(μ₃-S)(μ-S)₂(μ-SO₂)Cl₆(PMe₂Ph)₃]

A trinuclear rhenium sulfide cluster complex, [(Ph₃P)₂N][Re₃(μ₃-S)(μ-S)₃Cl₆(PMe₂Ph)₃], synthesized from Re₃S₇Cl₇, dimethylphenylphosphine, and [(Ph₃P)₂N]Cl is readily converted to a bridging SO₂ complex, [(Ph₃P)₂N][Re₃(μ₃-S)(μ-S)₂(μ-SO₂)Cl₆(PMe₂Ph)₃], by reaction with O₂. The oxygen atoms on the SO₂ ligand react with phosphines or phosphites to form phosphine oxides or phosphates, and the original cluster complex is recovered. The reaction course has been monitored by ³¹P NMR as well as by UV−vis spectroscopy. The catalytic oxygenation of PMePh₂ in the presence of the SO₂ complex shows that turnovers are 8 per hour at 23 °C in CDCl₃. The X-ray structures of the cluster complexes are described.