New Ruthenium Carbonyl Clusters Containing Unusual μ 5 -Sulfido-, μ 4 -Benzyne-, and Thianthrene-Derived Ligands: Insertion of Ruthenium into the Thianthrene Ring by C-S Activation Mohammad R. Hassan, ² Shariff E. Kabir,* ,² Brian K. Nicholson,* ,‡ Ebbe Nordlander, § and Md. Nazim Uddin ² Department of Chemistry, Jahangirnagar UniVersity, SaVar, Dhaka 1342, Bangladesh, Department of Chemistry, UniVersity of Waikato, Hamilton, New Zealand, and Inorganic Chemistry Research Group, Center for Chemistry and Chemical Engineering, Lund UniVersity, Box 124, SE 221 00, Lund, Sweden ReceiVed May 12, 2007 Treatment of [Ru 3 (CO) 12 ] with thianthrene in refluxing toluene afforded [(μ 4 -S)Ru 4 (μ-CO) 2 (CO) 9 (μ 4 - η 2 -C 6 H 4 )] (1), [(μ 5 -S)Ru 6 (μ-CO) 2 (CO) 15 (μ-η 3 -C 12 H 8 S)] (2), and [(μ 5 -S)Ru 5 (μ-CO) 2 (CO) 11 (μ-η 3 -C 12 H 8 S)- (μ 4 -η 2 -C 6 H 4 )] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [(μ 5 -S)Ru 5 (μ-CO) 2 (CO) 10 (μ-η 3 -C 12 H 8 S)(μ 4 -η 2 -C 6 H 4 )- (MeCN)] (4) in 73% yield. The reaction of 4 with P(OMe) 3 gave the substitution product [(μ 5 -S)Ru 5 - (μ-CO) 2 (CO) 10 (μ-η 3 -C 12 H 8 S)(μ 4 -η 2 -C 6 H 4 ){P(OMe) 3 }](5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a μ 4 -capping sulfido and a μ 4 -η 2 -benzyne ligand, whereas 3, 4, and 5 contain μ 5 -sulfido and μ 4 -η 2 -benzyne ligands. The latter three compounds provide rare examples of μ 5 -sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the μ 4 -η 2 -benzyne ligand is perpendicular to the Ru 4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne. Introduction The continuing considerable interest in transition metal complexes containing sulfur donor ligands is stimulated by their significant relevance to biological and industrial processes. 1 Sulfur-coordinated transition metal complexes are the active centers in many redox reactions in life processes. Such centers have been modeled with complexes containing cyclic polyden- tate sulfur ligands. 2 In addition, hydrodesulfurization (HDS) is also important for both industrial and environmental reasons; it is performed on a massive scale for the removal of sulfur from organosulfur compounds in petroleum-based feedstocks. 3,4 Given that aromatic S-heterocycles are among the most difficult impurities to remove, 5 a large number of model studies con- cerning transition metal thiophene, benzothiophene, and sub- stituted benzothiophene complexes have appeared in the litera- ture. 4-16 Stone and co-workers 13,14 were the first to demonstrate the reactivity of organometallic clusters with thiophenic mol- ecules, such as thiophene and benzothiophene, to produce ring- opened or desulfurized thiophene-containing transition metal complexes. 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