Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes: Synthesis and Structure of Thiolato-Bridged Diruthenium Cations of the Type [H2(arene)2Ru2(p-X-C6H4-S)]+ and [H(arene)2Ru2(p-X-C6H4-S)2]+

The cationic complexes [HRu2(η6-arene)2{μ2-(p-X-C6H4)-S}2]+ and [H2Ru2(η6-arene)2{μ2-(p-X-C6H4)-S}]+ (arene = 1,2,4,5-Me4C6H2 or C6Me6; X = Br and Me) are accessible in good yields from p-X-C6H4-SH with [H3Ru2(1,2,4,5-Me4C6H2)2][BF4] and [H3Ru2(C6Me6)2][BF4], respectively. The dibromo derivative [HRu2(C6Me6)2(p-Br-C6H4-S)2]+ is found to undergo double Suzuki coupling reactions with 3-thiophene boronic acid to give [HRu2(C6Me6)2(p-C4H3S-C6H4-S)2]+. This dibromo complex is a potential precursor for the insertion of dinuclear hydrido organometallic entities in the main chain of conjugated molecules.