Treatment of [Ru3(CO)12] with thianthrene in refluxing toluene afforded [( 4-S)Ru4( -CO)2(CO)9( 4- 2-C6H4)] (1), [( 5-S)Ru6( -CO)2(CO)15( - 3-C12H8S)] (2), and [( 5-S)Ru5( -CO)2(CO)11( - 3-C12H8S)( 4- 2-C6H4)] (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 [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4)(MeCN)] (4) in 73% yield. The reaction of 4 with P(OMe)3 gave the substitution product [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4){P(OMe)3}] (5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a 4-capping sulfido and a 4- 2-benzyne ligand, whereas 3, 4, and 5 contain 5-sulfido and 4- 2-benzyne ligands. The latter three compounds provide rare examples of 5-sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the 4- 2-benzyne ligand is perpendicular to the Ru4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne.
