Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS−)

Abstract

We have recently reported that cationic thiosulfonato ruthenium complexes [(p-cymene)Ru(bipy)(SSO₂Ar)]⁺ (bipy: 2-2′-bipyridine, Ar: phenyl or p-tolyl) react with thiolates (RS⁻, R = alkyl or aryl) by cleavage of the S–SO₂ bond and formation of a new S–S bond. In this work, we report that the outcome of the reaction is different if the hydrosulfide anion (R = H) is used, the product obtained being the hydrogen(sulfido) derivative [(p-cymene)Ru(bipy)(SH)]⁺. The bipy ligand is crucial in this result, and its replacement by ethylenediamine leads to a different product, the trisulfido-bridged dinuclear complex [[(p-cymene)Ru(en)(S)]₂S]²⁺. These two new species have been fully characterized, including by X-ray diffraction studies, and the two different mechanisms leading to their formation are discussed.