Synthesis, structure and reactivity of complexes containing [M(S2)2] fragments (M=Ru, Os; (S2)2−=1,2-benzenedithiolate (2−))

Subsequent addition of 1,2-benzenedithiol (S2–H2) and nBuLi to a solution of [Ru(NO)Cl3 · xMeOH] in THF afforded exclusively the monomeric species NBu4[RuII(NO)(S2)2] (1). Formation of dimeric (NBu4)2[RuII(NO)(S2)2]2 (2) has been confirmed when the deprotonated ligand S2–Li2 was added to [Ru(NO)Cl3 · xMeOH] and allowed to stir for 30 h. The monomer 1 undergoes aerial oxidation to give (NBu4)2[RuIV(S2)3] (3). The reaction between RuCl3 · xH2O and S2–H2 in the presence of NaOMe, afforded the dinulear RuIII species (NMe4)2[RuIII(S2)2]2 (4). A modified method for the preparation of 1 is being employed to synthesize the osmium analogue NBu4[Os(NO)(S2)2] (5) effectively. The solid state structures of 1, 2 and 3 were determined by X-ray crystal structure analysis. A comparison of relevant bond distance data suggests that 1,2-benzenedithiolate acts as an “innocent” ligand.