Syntheses of novel Fe/S clusters via reactions of Fe3(CO)12 and [Et4N][Ph2PCS2] with electrophiles

Reaction of Fe3(CO)12 with [NEt4][Ph2PCS2] in THF at room temperature forms a red-brown solution. Reactions of the solution with a series of electrophiles E-X (E-X = MeI, PhCH2Br, CH3COCl, PhCOCl) generate the corresponding clusters Fe2(CO)6(μ-k2P,C:k2S-Ph2PCSSE) (1, E = CH3; 2, E = CH2Ph; 3, E = COCH3; 4, E = COPh). The reaction of 4 with PPh3 in the presence of Me3NO affords the cluster [Fe2(CO)5(μ-k2P,C:k2S-Ph2PCSSCOPh)(k-PPh3)] (5) in which PPh3 is coordinated to the iron center with the PPh2 group. The tandem reaction of the solution with CS2 and with MeI gives the cluster Fe2(CO)5(μ-k2P,C:k2S-kS-Ph2PCSSC(double bond; length as m-dashS)SMe) (6). The tandem reaction of the solution with Fe3(CO)12 and with PPh2Cl forms the cluster Fe2(CO)6(μ-k2P,C:k2S-Ph2PCSS-k2S-)Fe2(CO)6(μ-PPh2) (7). The reaction of the solution with PhCCldouble bond; length as m-dashN(4-C6H4Cl) gives clusters Fe2(CO)6(μ-k2P,C:k2S-Ph2PCHS) (8), Fe2(CO)5(μ-k2P,C:k2S-kN-Ph2PCSSCPhdouble bond; length as m-dashN(4-C6H4Cl)) (9) and Fe2(CO)5(μ-k2P,C:k2S-kS-Ph2PCSN(4-C6H4Cl)CPhdouble bond; length as m-dashS) (10). Because the structures of all novel complexes have been unequivocally determined by X-ray crystallography, reactions of Fe3(CO)12 and [Et4N][Ph2PCS2] with electrophiles have provided new methods for synthesizing novel Fe/S clusters.