Syntheses of new Fe/S clusters via reactions of Fe3(CO)12 and salts of heteroallyl anions of type [GCS2]− (G = Ph2PS, ArCOCH2, 2-C5H4NNH and 2-C3H2NSNH) with electrophiles

The reaction of Fe3(CO)12 and [NEt4][GCS2] with an electrophile CH3I in THF affords complex Fe2(CO)6(μ-GC(S)SCH3) (G = Ph2PS, 1). The reaction of Fe3(CO)12 with PhCOCH2CS2H and NEt3 forms a red-brown solution of [HNEt3][Fe2(CO)6(μ-GCS2)] identified by IR and ESI-MS (G = PhCOCH2). The reactions of the solution with a series of electrophiles E–X such as CH3I, PhCH2Br and CH2CHCH2Br produce complexes Fe2(CO)6(μ-GC(S)SE) (2, E = CH3; 3, E = CH2Ph; 4, E = CH2CHCH2). In the absence of NEt3, the reaction of Fe3(CO)12 and PhCOCH2CS2H gives complex Fe2(CO)6(μ-S2CCHCOPh) (5). The reaction of GCS2H with NEt3, Fe3(CO)12 and CH3I yields complexes Fe2(CO)6(μ-GC(S)SCH3) (G = 4-MeOC6H4COCH2, 6; G = C5H5FeC5H4COCH2, 7). The reaction of Fe(C5H4COCH2CS2H)2, NEt3 and Fe3(CO)12 with CH3I affords complex Fe[(μ-C5H4COCH2C(S)SCH3)Fe2(CO)6]2 (8). Unlike the above-mentioned cases, the reaction of Fe3(CO)12 and [HNEt3][GCS2] (G = 2-C5H4NNH, 2-C3H2NSNH) with PhCOCl generates the corresponding complexes Fe2(CO)5(μ-k2N,S:k2C-2-C5H4NN(COPh)CS)(μ-k2S-SCOPh) (9) and Fe2(CO)5(μ-k2N,S:k2C-2-C3H2NSN(COPh)CS)(μ-k2S-SCOPh) (10). All new complexes have been characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy as well as 31P NMR spectroscopy for 1, structures of them have been unequivocally determined by X-ray crystallography.

Graphical abstractTwo new routes to novel Fe/S clusters have been exploited. Reactions of cluster anions of [(μ-GCS2)Fe2(CO)6]− (G = Ph2PS, ArCOCH2) and [(μ-G′NHCS)Fe2(CO)5(μ-S−)] (G′ = 2-C5H4N, 2-C3H2NS) generated from Fe3(CO)12 and heteroally anions of GCS2− and G′NHCS2− in THF with a series of electrophiles afford novel cluster complexes.Figure optionsDownload full-size imageDownload as PowerPoint slide