Triosmium clusters containing bridging dppm and EPh (E = S, Te) ligands: X-ray structures of [(μ-H)Os3(CO)7(μ-SPh){μ3-η4-Ph2PCHP(Ph)C6H4}], [Os3(CO)8(μ-SPh)2(μ-dppm)] and [Os3(CO)8(μ-TePh)2(μ-dppm)]

Heating [Os3(CO)10(μ-dppm)] (1) with two equivalents of PhSSPh in toluene under reflux provided three new triosmium compounds [(μ-H)Os3(CO)7(μ-SPh){μ3-η4-Ph2PCHP(Ph)C6H4}] (2), [Os3(CO)8(μ-SPh)2(μ-dppm)] (3) and [(μ-H)Os3(CO)7(μ-η2-SC6H4)(μ-SPh)(μ-dppm)] (4) in 20%, 21% and 26% yields, respectively. In contrast, a similar reaction of 1 with two equivalents of PhTeTePh in refluxing toluene gave the binuclear compound [Os2(CO)4(μ-TePh)2(μ-dppm)] (6) in 15% yield, and two 50 electron isomeric compounds 5 and 7 with the formula [Os3(CO)8(μ-TePh)2(μ-dppm)] in 20% and 23% yields, respectively. Thermolysis of 3 at 110 °C afforded 4 in 53% yield which on further thermolysis in refluxing octane at 128 °C gave 2 in 45% yield. Thermolysis of 3 in refluxing octane also gave 2 in 50% yield. The new compounds, 2–7, were all spectroscopically characterized, and the X-ray structures of 2, 3 and 7 have been determined. Compound 2 contains a bridging SPh ligand and a μ3,η4-Ph2PCHP(Ph)C6H4 ligand, formed by two kinds of C–H activation, including orthometallation of a phenyl group as well as an unusual activation of the methylene group of the dppm ligand. The molecular structure of 3 reveals that two SPh groups span the open Os–Os edge of the Os3 triangle, while the dppm ligand bridges one of the closed Os–Os edges. In compound 7, one TePh group spans the open Os–Os edge, while the other spans one of the two closed Os–Os edges and the dppm ligand bridges the third Os–Os vector.