SYNTHESIS OF THE NOVEL THIOLATO-BRIDGED AND OXO-CAPPED TRIMETALLIC CLUSTERS (ETA(5)-R'C5H4)(CO)(2)MFE2(MU(3)-O)-(MU-RS)(CO)(6) VIA REACTIONS OF [ET3NH][(MU-RS)(MU-CO)-FE-2(CO)(6)] WITH TRIPLY BONDED DIMERS [(ETA(5)-R'C5H4)(CO)(2)M](2) (M = MO, W) AND SUBSEQUENT TREATMENT WITH AIR - CRYSTAL-STRUCTURES OF )-MEO2CC5H4)(CO)(2)MOFE2(MU(3)-O)(MU-T-BUS)(CO)(6) AND

The complex salts [Et3NH][(mu-RS)(mu-CO)Fe-2(CO)(6)] (1: R = Et, t-Bu, Ph), prepared from Fe-3(CO)(12), RSH, and Et3N, react in situ with th e triply bonded dimers [(eta(5)-R'C5H4)(CO)(2)M](2) (2: M = Mo, W; R' = H, MeCO, MeO2C, EtO2C) followed by treatment with air to give the se ries of novel clusters (eta(5)-R'C5H4)(CO)(2)MoFe2(mu(3)-O)(mu-RS)(CO) (6) (compound, R, R': 3a, Et, H; 3b, t-Bu, H; 3c, Et, MeCO; 3d, t-Bu, MeO2C; 3e, Ph, MeO2C; 3f, Et, EtO2C; 3g, t-Bu, EtO2C; 3h, Ph, EtO2C) i n 26-37% yields and (eta(5)-R'C5H4)(CO)(2)WFe2(mu(3)-O)(mu-RS)(CO)(6) (compound, R, R': 3i, Et, MeO2C; 3j, t-Bu, MeO2C; 3k, Et, EtO2C) in 12 -17% yields. Single-crystal X-ray diffraction analyses of 3d and 3k; c onfirmed that (i) these clusters consist of the M-S (M = Mo, W) edge-o pened square-pyramidal cluster skeleton MFe2SO with the M atom occupyi ng its apical position and the Fe2OS atoms constructing its pyramid ba se and (ii) clusters 3d and 3k are single isomers in which the t-Bu an d Et groups are bonded to the bridged S atoms by an equatorial type of bond.