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)(SSO(2)Ar)](+) (bipy 2-2'-bipyridine, Ar phenyl or p-tolyl) react with thiolates (RS(-), R = alkyl or aryl) by cleavage of the S-SO(2) 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)](2)S](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.