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.

Studies of Iron(III) Porphyrinates Containing Silanethiolate Ligands

“…Even in ruthenium chemistry, where binding of H 2 S is well established, 43–49 examples involving porphyrinate ligands are unknown. James has reported several thiol adducts of [Ru II (TMP)] (TMP = meso -tetramesitylporphine), although analogous reactions with H 2 S did not afford well-defined species.…”

“…In all these previous reports, the difficulty in preparing and isolating H 2 S/HS – species of iron porphyrinates has precluded detailed examinations of their reactivity and spectroscopy. Even in ruthenium chemistry, where binding of H 2 S is well established, − examples involving porphyrinate ligands are unknown. James has reported several thiol adducts of [Ru II (TMP)] (TMP = meso -tetramesitylporphine), although analogous reactions with H 2 S did not afford well-defined species. , …”