Synthesis and structure of the organometallic MFe2(mu3-S)2 clusters (M = Mo or Fe)

New organometallic clusters with the MFe2(mu3-S)2 core (M = Mo or Fe) have been synthesized from inorganic MoFe3S4] or Fe4S4] clusters under high pressure CO. The reaction of (Cl4-cat)2Mo2Fe6S8(PR3)6R = Et, (n)Pr] with high pressure CO produced the crystalline MoFe2S2]4+ clusters, (Cl4-cat)Mo(O)Fe2S2(CO)(n)(PR3)6-nn= 4, Et =I, (n)Pr =II; n = 5, Et =III] after flash column chromatography. The similar MoFe2S2]4+ cluster, (Cl4-cat)2MoFe2S2(CO)2(depe)(2)(IV), also has been achieved by the reactions of (Cl4-cat)MoFe3S3(CO)6(PEt3)2 with depe by reductive decoupling of the cluster. For the Fe3(mu3-S)2]4+ cluster, Fe4S4(PcHex3)4](BPh4) was reacted with high pressure CO to produce a new Fe3S2(CO)7(PcHex)(2)(V) compound. These reactions generalized the preparation of organometallic compounds from inorganic clusters. All the compounds have been characterized by single crystal X-ray crystallography. A possible reaction pathway for the synthesis of the MFe2(mu3-S) clusters (M = Mo or Fe) has also been suggested.