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

The Ru(II)-arene complex (CymRuCl)(2)(mu -Cl)(2) (Cym=eta (6)-p-MeC6H4Pri) dissolved in CH2Cl2 reacted with H2S gas or in situ-generated H2Se to affor d the hydrosulfido- and hydroselenido-bridged diruthenium complexes (CymRuC l)(2)(mu -EH)(2) (E=S 2, Se 3). Complexes 2 and 3 were converted further in to the cubane-type tetraruthenium sulfido and selenido clusters (CymRu)(4)( mu (3)-E)(4) (E=S 4, Se 5) by treatment with NEt3 in benzene. The reactions are presumed to proceed via coupling of the diruthenium species (CymRu)(2) (mu -E)(2) initially formed by dehydrochlorination of 2 and 3. The structur es of new compounds 2, 3, 4 and 5 have been determined in detail by X-ray c rystallography.