PREPARATION OF THE HYDROSULFIDO-BRIDGED DIRUTHENIUM COMPLEX 5)-C(5)ME(5))RUCL(MU-SH)(2)RU(ETA(5)-C(5)ME(5))CL] AND ITS TRANSFORMATION INTO A CUBANE-TYPE TETRARUTHENIUM SULFIDE CLUSTER OR TRIANGULAR HETEROMETALLIC RHRU2 SULFIDE CLUSTER

The hydrosulfido-bridged diruthenium complex [CpRuCl(mu-SH)(2)RuCp*Cl ] (4; Cp = eta(5)-C(5)Me(5)) was obtained by the reaction of either [ (CpRu)(4)(mu(3)-Cl)(4)] (1) or [Cp*RuCl(mu-Cl)(2)-RuCp*Cl] with exces s H2S gas, while the reactions of 1 with thiols resulted in the format ion of the thiolato-bridged diruthenium complexes [CpRuCl(mu-SR)(2)Ru CpCl] (R = Et (5a), C6H4-Me-p). When a solution of 4 in toluene was h eated at reflux, the cubane-type tetraruthenium sulfide cluster [(CpR u)(4)(mu(3)-S)(4)]Cl-2 (6) was produced. On the other hand, treatment of 4 with 2 molar equiv of [RhCl(PPh(3))(3)] in THF at room temperatur e afforded the triangular heterometallic sulfide cluster [(CpRu)(2)(m u(2)-H)(mu(3)-S)(2)RhCl2(PPh(3))] (10). X-ray analyses have been under taken to determine the detailed structures for 4, 5a, 6, and 10.