Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes: Synthesis and Structure of Thiolato‐Bridged Diruthenium Cations of the Type [H 2 (arene) 2 Ru 2 ( p ‐X−C 6 H 4 −S)] + and [H(arene) 2 Ru 2 ( p ‐X−C 6 H 4 −S) 2 ] +

The cationic complexes [HRu 2 (η 6 ‐arene) 2 {μ 2 ‐( p ‐X−C 6 H 4 )−S} 2 ] + and [H 2 Ru 2 (η 6 ‐arene) 2 {μ 2 ‐( p ‐X−C 6 H 4 )−S}] + (arene = 1,2,4,5‐Me 4 C 6 H 2 or C 6 Me 6 ; X = Br and Me) are accessible in good yields from p ‐X−C 6 H 4 −SH with [H 3 Ru 2 (1,2,4,5‐Me 4 C 6 H 2 ) 2 ][BF 4 ] and [H 3 Ru 2 (C 6 Me 6 ) 2 ][BF 4 ], respectively. The dibromo derivative [HRu 2 (C 6 Me 6 ) 2 ( p ‐Br−C 6 H 4 −S) 2 ] + is found to undergo double Suzuki coupling reactions with 3‐thiophene boronic acid to give [HRu 2 (C 6 Me 6 ) 2 ( p ‐C 4 H 3 S−C 6 H 4 −S) 2 ] + . This dibromo complex is a potential precursor for the insertion of dinuclear hydrido organometallic entities in the main chain of conjugated molecules. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)