The thermal reaction of [(cymene)RuCl2]2 and tetramethylthiophene (TMT) gives [(TMT)RuCl2]2 (1). Treatment of 1 with silver salts in the presence of various ligands gives salts of [(TMT)RuL3]2+ where L3 = (H2O)3, (CH3CN)3, and TMT. A crystallographic study demonstrated that [(TMT)2Ru](BF4)2·2CH3NO 2 adopts a sandwich structure with sulfur atoms sited cis on the pseudooctahedron. Cyclic voltammetry studies show that [(TMT)2Ru]2+ undergoes two reversible one-electron reductions. Solutions of 1 and phosphine and amine donors react to give well-behaved monometallic derivatives of the type (TMT)RuCl2L where L is PR3 and NH2C6H4Me. For bulky L = PPh3 and P(C6H4Me)3, variable-temperature NMR studies demonstrate hindered rotation about the Ru-P and Ru⋯TMT axes. Treatment of 1 with (Me3Si)2S gives the cluster [(TMT)RuCl]3S+ whose PF6- salt was examined by X-ray crystallography. The cluster is comprised of three conjoined pseudooctahedral Ru centers bridged by one μ3-S and three μ-Cl atoms.
ASJC Scopus subject areas
- Colloid and Surface Chemistry