Unexpected Preparation of Butterfly Fe/S Cluster Complexes Containing a Quaternary Phosphorus Atom via Reactions of the Anions (<i>μ</i><i>-</i>RS)(<i>μ</i><i>-</i>S^-)Fe₂(CO)₆ and (<i>μ</i><i>-</i>RS)(<i>μ</i><i>-</i>S^-)[Fe₂(CO)₆]₂(<i>μ</i>₄<i>-</i>S) with Diphenylchlorophosphine

Six new butterfly Fe/S cluster complexes, (μ-RS)(η1-Ph2PS-η1)[Fe2(CO)6] (3, R = Me; 5, R = Ph), (μ-RS)(η1-Ph2PS-η1)[Fe2(CO)5(Ph2PY)] (4, R = Me, Y = Cl; 6, R = Y = Ph), and (μ-RS)(η1-Ph2PS-η2)[Fe2(CO)6](μ4-S)[Fe2(CO)5] (7, R = n-Bu; 8, R = Ph), were unexpectedly prepared by a “one-pot” synthetic method involving reactions of the in situ generated S-centered monoanions (μ-RS)(μ-S-)Fe2(CO)6 (1) and (μ-RS)(μ-S-)[Fe2(CO)6]2(μ4-S) (2) with Ph2PCl. While the possible mechanisms for the unexpected reactions are suggested, the structures of products 3−8 have been fully characterized.