Preparation of hydrosulfido- and hydroselenido-bridged diruthenium complexes with π-arene co-ligands and their conversion into new cubane-type sulfido or selenido clusters

Abstract

The Ru(II)-arene complex (CymRuCl)₂(μ-Cl)₂ (Cym = η⁶-p-MeC₆H₄Prⁱ) dissolved in CH₂Cl₂ reacted with H₂S gas or in situ-generated H₂Se to afford the hydrosulfido- and hydroselenido-bridged diruthenium complexes (CymRuCl)₂(μ-EH)₂ (E = S 2, Se 3). Complexes 2 and 3 were converted further into the cubane-type tetraruthenium sulfido and selenido clusters (CymRu)₄(μ₃-E)₄ (E = S 4, Se 5) by treatment with NEt₃ in benzene. The reactions are presumed to proceed ia coupling of the diruthenium species (CymRu)₂(μ-E)₂ initially formed by dehydrochlorination of 2 and 3. The structures of new compounds 2, 3, 4 and 5 have been determined in detail by X-ray crystallography.