Cluster construction by reactions of an isomeric pair of trinuclear clusters containing a tetrathiotungstate fragment, [{Cp ' Ru(Co)}(2){W(mu-S)(4)}]and [{Cp ' Ru(CO)}(2){W(= S)(u(3)-S)(mu-S)(2)}] (Cp ' = eta(5)-C5Me5, eta(5)-C5Me4Et), with platinum complexes

The reactions of the isomeric pair of trinuclear clusters [{Cp'Ru(CO)}(2){W (mu -S)(4)}] (3) and [{Cp'Ru(CO)}(2){W(=S)(mu (3)-S)(mu -S)(2)}] (4) with 1 equiv of [PtMe2(cod)] gave the respective tetranuclear clusters [{Cp'Ru(CO )}(2){W(mu (3)-S)(2)(mu -S)(2)}(PtMe2)] (5) and [{Cp'Ru(CO)}(2){W(=S)-(mu ( 3)-S)(3)}(PtMe2)} (6) (Cp' = eta 5-C5Me5 (=Cp*), eta (5)-C5Me4Et) containin g a tetrathiotungstate fragment as the main products, which corresponds to an isomeric pair. The pentanuclear cluster [{Cp'Ru(CO)}(2){W(mu (3)-S)(4)}( PtMe2)(2)] (7) was obtained by the reaction of [{Cp'Ru(CO)}(2)-{W(mu -S)(4) }] (3) with 2 equiv of [PtMe2(cod)]. Treatment of [{Cp*Ru(CO)}(2){W(mu (4)- S)(2)(mu -S)(2)}-(PtMe2)] (5a) with excess HCl underwent monochlorination o f the methyl ligand in the PtMe2 moiety to give [{Cp*Ru(CO)}(2){W(mu (3)-S) 2(mu -S)(2)}(PtClMe)] (8) selectively. In the reaction of [{Cp*Ru(CO)}(2){W (mu (3)-S)(4)(PtMe2)(2)] (7a) with 1 equiv of HCl, monochlorination at one platinum center took place to give[{Cp*Ru(CO)}(2){W(mu (3)-S)(4)}(PtClMe)(P tMe2)] (10) quantitatively, whereas the reaction of Ma with excess HCl took place with monochlorination at each platinum center to give [{Cp*Ru(CO)}(2 ){W(mu (3)-S)(4)}(PtClMe)(2)] (9). the trinuclear cluster [{Cp'Ru(CO)}(2){W (mu -S)(4)}] (3) reacted with the platinum(0) complex [Pt(C2H4)(PPh3)(2)] t o give the novel pentanuclear cluster [{Cp'Ru(CO)}(WS4)(Cp'Ru{Pt-2(PPh3)2(m u -CO)}] (11). The product 11 has a new platinum-platinum bond bridged by a carbonyl ligand which is originally located on a ruthenium center. The tet rathiotungstate ligand in 11 bridges the ruthenium fragment Cp'Ru(CO) and t he three-membered metallacycle (Cp'Ru){Pt(PPh3)}(2)-(mu -CO).