Synthesis and characterization of double- and triple-butterfly Fe/S cluster complexes obtained from the novel butterfly cluster anions {(mu-RS)(mu-CO)[Fe-2(CO)(6)](2)(mu(4)-S)}(-) and (mu-RS)(mu-S-)[Fe-2(CO)(6)](3)(mu(4)-S)(2). Crystal structures of (mu-MeS)(mu-PhNHC=S)[Fe-2(CO)(6)](2)(mu(4)-S), (mu-MeS)(mu-MeSC=S)[Fe-2(CO)(6)]2(()mu(4)-S), and (mu-PhCH2S)(2)[Fe-2(CO)(6)](3)(mu(4)-S)(2)

The novel reaction of (mu-RS)(mu-S-)Fe-2(CO)(6) (1) with Fe-3(CO)(12) gives a new type of anion, {(mu-Rs)(mu-CO)[Fe-2(CO)(6)](2)(mu(4)-S)}(-) (4). Whi le anions 4 (R = Me, Et) react with PhNCS/CF3-CO2H to give the neutral doub le-cluster complexes (mu-RS)(mu-PhNHC=S)[Fe-2(CO)(6)](2)(mu(4)-S) (6, R = M e; 7, R = Et), the reaction of 4 (R = Me, Ph, p-MeC6H4) with CS2/MeI or PhC H2Br affords the neutral double-cluster complexes (mu-RS)(mu-MeSC=S)[Fe-2(C O)(6)](2)(mu(4)-S) (8, R = Me;10, R = p-MeC6H4; 12, R = Ph), and (mu-RS)(mu -MeSC=S)[Fe-2(CO)(6)](2)(mu(4)-S) (9, R = Me; 11, R = p-MeC6H4), respective ly. More interestingly, reaction of anions 4 with mu-S2Fe2(CO)(6) produces another new type of anion, (mu-RS)(mu-S-)[Fe-2(CO)(6)](3)(mu(4)-S)(2) (5),w hich reacts further with MeI, EtBr, or PhCH2Br to give the neutral triple-c luster complexes (mu-RS)(mu-MeS)[Fe-2-(CO)(6)](3)(mu(4)-S)(2) (13, R= Me; 1 4, R p-MeC6H4), (mu-p-MeC6H4S)(mu-EtS)[Fe-2(CO)(6)](3)(mu(4)-S)(2) (15), an d (mu-PhCH2S)(2)[Fe-2(CO)(6)](3)(mu(4)-S)(2) (16), respectively. All these new double- and triple-butterfly clusters have been characterized by combus tion analyses and spectroscopy as well as by X-ray diffraction for clusters 6, 8, and 16.