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)Cl-2](2), [Ru(p-(MeC6H4Pr)-Pr-i)Cl-2](2), [Ru(1,2,4,5-C6H2Me4)Cl-2](2), and [Ru(C6Me6)Cl-2](2) react in ethanol with p-bromothiophenol to give the corresponding cationic complexes [Ru-2(C6H6)(2)(p-S-C6H4-Br)(3)](+) (1), [Ru-2(p-(MeC6H4Pr)-Pr-i)(2)(p-S-C6H4-Br)(3)](+) (2), [Ru-2(1,2,4,5-C6H2Me4)(2)(p-S-C6H4-Br)(3)](+) (3), and [Ru-2(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. (C) 2003 Elsevier B.V. All rights reserved.