SYNTHESIS AND CHARACTERIZATION OF SULFUR IRON/MOLYBDENUM (TUNGSTEN) CLUSTER COMPOUNDS CONTAINING FUNCTIONALLY-SUBSTITUTED CYCLOPENTADIENYL LIGAND - SINGLE-CRYSTAL STRUCTURE OF 5)H(4))(2)(MU(3)-CO)(2)MO2FE2(MU(3)-S)(2)(CO)(6)]/

Reaction of mu-S-2-Fe-2(CO)(6) with Mo=Mo triply bonded dimers [eta(5) -RC(5)H(4)(CO)(2)Mo](2) in CH2Cl2 at room temperature gave clusters (5 )H(4))(2)(mu(3)-CO)(2)Mo2Fe2(mu(3)-S)(2)(CO)(6)] (1a, R = MeCO; 1b, R = MeO(2)C; 1c, R = EtO(2)C), whereas mu-S2Fe2(CO)(6) reacted with W=W triply bonded dimers [eta(5)-RC(5)H(4)(CO)(2)W](2) to afford the clust ers C(5)H(4))(2)(mu(3)-CO)(2)W2Fe2(mu(3)-S)(2)(CO)(6)] (2a, R = MeO(2) C; 2b, R = EtO(2)C) and [[eta(5)-RC(5)H(4)(CO)(2)]2W2Fe(mu(3)-S)(CO)(3 )] (3a, R = MeO(2)C; 3b, R = EtO(2)C). While clusters 1a-1c could also be produced by reaction of mu-S2Fe2(CO)(6) with Mo-Mo singly bonded d imers [eta(5)-RC(5)H(4)(CO)(3)Mo](2) in refiuxing toluene, the reactio n with W-W singly bonded dimers [eta(5)-RC(5)H(4)(CO)(3)W](2) failed t o give the corresponding dimers 2a-2b and 3a-3b. In addition, cluster 1a reacted with NaBH4 in MeOH at room temperature to give the bis-hydr oxyl derivative OH)C5H4](2)(mu(3)-CO)(2)Mo2Fe2(mu(3)-S)(2)(CO)(6)] (4) , whereas it afforded mono- and bis-hydrazone derivatives [(eta(5)-MeC OC(5)H(4)) NC(Me)C5H4](mu(3)-CO)(2)Mo2Fe2(mu(3)-S)(2)(CO)(6)] (5) and Me)C5H4](2)(mu(3)-CO)(2)Mo2Fe2(mu(3)-S)(2)(CO)(6)] (6) when reacted wi th 2,4-dinitrophenyhydrazine in EtOH at room temperature. All the new clusters were characterized by elemental analysis and spectroscopic me thods, as well as for 1b by X-ray diffraction techniques. Copyright (C ) 1996 Elsevier Science Ltd