Palladium-Catalyzed Reactions of [Et3NH]+ Salts of [(μ-RS)(μ-CO)Fe2(CO)6]− Anions with Iodo-Aromatic Compounds To Give the Corresponding Butterfly μ‑Acyl Fe/S Cluster Complexes

Interestingly, the intermediate salts A·[Et3NH] (A = (μ-RS)­(μ-CO)­Fe2(CO)6; R = i-Pr, sec-Bu, cy-C6H11, p-MeC6H4) prepared from Fe3(CO)12, RSH, and Et3N were found to react in situ with iodobenzene or its substituted derivatives in the presence of the catalyst precursor Pd­(PPh3)4 to give the benzoyl type μ-acyl complexes (μ-RS)­(μ-ArCO)­Fe2(CO)6 (Ar = phenyl or substituted phenyl), whereas the in situ reactions of A·[Et3NH] with iodo-substituted aromatic heterocycles under the same conditions afforded the corresponding heterocyclic type μ-acyl complexes (μ-RS)­(μ-ArCO)­Fe2(CO)6 (Ar = heterocyclic or benzoheterocyclic group). Particularly worth noting is that such Pd-catalyzed C–C bond cross-coupling reactions are the first examples of catalytic reactions regarding A·[Et3NH] salts reported so far. In addition, all the prepared new μ-acyl complexes and the three new intermediate salts A·[Et3NH] (R = i-Pr, sec-Bu, cy-C6H11) were isolated and structurally characterized, while a possible pathway for such type Pd-catalyzed reactions regarding A·[Et3NH] salts is suggested.