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)2C6H4]

The [Et3NH](+) salts of mu -CO anions [(mu -RE)(mu -CO)Fe-2(CO)(6)](-) (E = S, Se) prepared from Fe-3(CO)(12), REH (c = S,Se) and Et3N reacted with mu -S2Fe2(CO)(6) and subsequent treatment of the intermediate [Et3NH](+) salts of S-centered anions (mu -RE)(mu -S-)[Fe-2(CO)(6)](2)(mu (4)-S) with MeI, PhCH2Br, p-(BrCH2)(2)C6H4 or 1,3,5-(BrCH2)(3)C6H3 to give a series of mu (4)-S-containing double and multiple butterfly clusters (mu -RE)(mu -MeS)[Fe-2(CO)(6)](2)(mu (4)-S) (7-9, RE = t-BuS, PhSe, p-MeC6H4Se), (mu -p-MeC6H4Se)(mu -PhCH2S)[Fe-2(CO)(6)](2)(mu (4)-S) (11), {(mu -t-BuS)[Fe-2 (CO)(6)](2)(mu (4)-S)}(2)[(mu -p-(SCH2)(2)C6H4] (12) and {(mu -t-BuS)[Fe-2(CO)(6)](2)(mu (4)-S)}(3)[mu -1,3,5-(SCH2)(3)C6H3] (13), whereas the [MgBr](+) salts of mu -CO anions [(mu -RTe)(mu -CO)Fe-2(CO)(6)](-) prepared from Grignard reagents RMgBr and elemental Te followed by treatment of the intermediates RTeMgBr with Fe-3(CO)(12), reacted with S2Cl2 to afford a series of RTe-containing and mu -S-S-mu bridged double butterfly clusters [(mu -RTe) Fe-2(CO)(6)](2)(mu -S-S-mu) (14-17, R = Et, i-Bu, Ph, p-MeC6H4). Similarly, the RTe- and mu (4)-S-containing double butterfly cluster (mu -p-MeC6H4Te)(mu -MeS)[Fe-2(CO)(6)]2(mu (4)-S) (10) could be prepared by reaction of the [MgBr](+) salt of mu -CO anion (mu -p-MeC6H4Te)(mu -CO)Fe-2(CO)(6)](-) with mu -S2Fe2(CO)(6) followed by treatment with Mel. All these new clusters 7-17 have been characterized by combustion analysis, IR, H-1-NMR, Se-77-NMR and Te-125-NMR spectroscopies, as well as by X-ray diffraction analyses for 9 (RE = p-MeC6H4Se) and 12 (RE = t-BuS). (C) 2001 Elsevier Science B.V. All rights reserved.