Tetranuclear butterfly cluster derivatives of SMe2. Preparation and structures of Ru4(CO)13(SMe2), H2Ru4(CO)12(SMe2), and HRu3Co(CO)12(SMe2)

Article abstract of DOI:10.1021/om00051a033

The carbonyl clusters Ru₄(CO)₁₃(SMe₃) (1), H₂Ru₄(CO)₁₂(SMe₂) (2), and HRu₃Co(CO)₁₂(SMe₂) (3) have been obtained in reactions between dimethyl sulfide and tri- or tetranuclear metal carbonyl clusters. These compounds have been characterized by X-ray diffraction studies. 1 crystallizes in space group P2₁/n with a = 9.406 (3) ?, b = 15.393 (6) ?, c = 15.812 (6) ?, β = 92.23 (3)°, and Z = 4; 2, in space group P2₁ with a = 8.18 (1) ?, 6 = 15.86 (2) ?, c = 9.55 (1) ?, β = 114.6 (1)°, and Z = 2; 3, in space group P2₁/n with a = 9.349 (4) ?, b = 16.259 (7) ?, c = 14.469 (6) ?, β = 92.04 (3)°, and Z = 4. The compounds are butterfly clusters, in which the four-electron SMe₂ ligand bridges the wing-tip positions. In 1 and 3 one of the carbonyls bridges the hinge of the butterfly; otherwise the compounds contain only terminal carbonyls. The hydrides occupy a wing and the hinge Ru-Ru bond in 2 and a wing Ru-Co bond in 3. In 3 the cobalt atom is in a hinge position. The chalcogenide derivatives of tetranuclear Ru-Co-Rh cluster compounds show a structural trend depending on the metal composition. Terminal coordination (Co₄, RuCo₃, and RuCo₂Rh), butterfly structures (Ru₄ and Ru₃Co), or dimerization of clusters (RuRh₃) is found.