Synthesis and structural characterisation of new cationic dinuclear ruthenium(II) thiolato complexes of the type [Ru2(η6-arene)2(μ-p-S–C6H4–Br)3]+

Dinuclear dichloro complexes [Ru(C6H6)Cl2]2, [Ru(p-MeC6H4 iPr)Cl2]2, [Ru(1,2,4,5-C6H2Me4)Cl2]2, and [Ru(C6Me6)Cl2]2 react in ethanol with p-bromothiophenol to give the corresponding cationic complexes [Ru2(C6H6)2(p-S–C6H4–Br)3]+ (1), [Ru2(p-MeC6H4 iPr)2(p-S–C6H4–Br)3]+ (2), [Ru2(1,2,4,5-C6H2Me4)2(p-S–C6H4–Br)3]+ (3), and [Ru2(C6Me6)2(p-S–C6H4–Br)3]+ (4), which can be isolated in quantitative yield as their chloride salts. X-ray structure analysis of these complexes shows that the nature of the arene ligand influences the folding of the p-S–C6H4–Br units. In 1, where the less hindered arene ligand is present, the three phenyl rings of the thiolato units are not constrained to a coplanar arrangement, whereas in 4 the C6Me6 forces the three phenyl rings to be in perfect planarity. Complexes 2 and 3 show an intermediary arrangement. [Copyright &y& Elsevier]