Synthesis of double and multiple butterfly Fe/E (E=S, Se, Te) cluster complexes via reactions of complex anions [(μ-RE)(μ-CO)Fe2(CO)6]− (E=S, Se, Te). Crystal structures of (μ-p-MeC6H4Se)(μ-MeS)[Fe2(CO)6]2(μ4-S) and {(μ-t-BuS)[Fe2(CO)6]2(μ4-S)}2[(μ-p-SCH2

The [Et3NH]+ salts of μ-CO anions [(μ-RE)(μ-CO)Fe2(CO)6]− (E=S, Se) prepared from Fe3(CO)12, REH (R=S,Se) and Et3N reacted with μ-S2Fe2(CO)6 and subsequent treatment of the intermediate [Et3NH]+ salts of S-centered anions (μ-RE)(μ-S−)[Fe2(CO)6]2(μ4-S) with MeI, PhCH2Br, p-(BrCH2)2C6H4 or 1,3,5-(BrCH2)3C6H3 to give a series of μ4-S-containing double and multiple butterfly clusters (μ-RE)(μ-MeS)[Fe2(CO)6]2(μ4-S) (7–9, RE=t-BuS, PhSe, p-MeC6H4Se), (μ-p-MeC6H4Se)(μ-PhCH2S)[Fe2(CO)6]2(μ4-S) (11), {(μ-t-BuS)[Fe2 (CO)6]2(μ4-S)}2[(μ-p-(SCH2)2C6H4] (12) and {(μ-t-BuS)[Fe2(CO)6]2(μ4-S)}3[μ-1,3,5-(SCH2)3C6H3] (13), whereas the [MgBr]+ salts of μ-CO anions [(μ-RTe)(μ-CO)Fe2(CO)6]− prepared from Grignard reagents RMgBr and elemental Te followed by treatment of the intermediates RTeMgBr with Fe3(CO)12, reacted with S2Cl2 to afford a series of RTe-containing and μ-S–S-μ bridged double butterfly clusters [(μ-RTe) Fe2(CO)6]2(μ-S–S-μ) (14–17, R=Et, i-Bu, Ph, p-MeC6H4). Similarly, the RTe- and μ4-S-containing double butterfly cluster (μ-p-MeC6H4Te)(μ-MeS)[Fe2(CO)6]2(μ4-S) (10) could be prepared by reaction of the [MgBr]+ salt of μ-CO anion (μ-p-MeC6H4Te)(μ-CO)Fe2(CO)6]− with μ-S2Fe2(CO)6 followed by treatment with MeI. All these new clusters 7–17 have been characterized by combustion analysis, IR, 1H-NMR, 77Se-NMR and 125Te-NMR spectroscopies, as well as by X-ray diffraction analyses for 9 (RE=p-MeC6H4Se) and 12 (RE=t-BuS).