Preparation of the hydrosulfido-bridged diruthenium complex [(eta(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 [Cp*RuCl(mu-SH)(2)RuCp*Cl] (4; Cp* = eta(5)-C(5)Me(5)) was obtained by the reaction of either [(Cp*Ru)(4)(mu(3)-Cl)(4)] (1) or [Cp*RuCl(mu-Cl)(2)-RuCp*Cl] with excess H2S gas, while the reactions of 1 with thiols resulted in the formation of the thiolato-bridged diruthenium complexes [Cp*RuCl(mu-SR)(2)RuCp*Cl] (R = Et (5a), C6H4-Me-p). When a solution of 4 in toluene was heated at reflux, the cubane-type tetraruthenium sulfide cluster [(Cp*Ru)(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 temperature afforded the triangular heterometallic sulfide cluster [(Cp*Ru)(2)(mu(2)-H)(mu(3)-S)(2)RhCl2(PPh(3))] (10). X-ray analyses have been undertaken to determine the detailed structures for 4, 5a, 6, and 10.