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The novel reactions of cluster salts [(μ-RS)Fe2(CO)6(μ4-CS2)Fe2(CO)6][Et3NH] with Ph2PCl, via the insertion of the PPh2 group into an activated C–S bond, afford the unprecedented tetrairon complexes with the unique SCPPh2S ligand which is coordinated to (μ-RS)Fe2(CO)6 and Fe2(CO)6 units in a μ4-k2C:k4S,S′ mode (R = Ph, CH3O2CCH2).
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