RING-OPENING AND CARBONYLATION OF 3,3-DIMETHYLTHIETANE LIGANDS IN RUTHENIUM CARBONYL CLUSTER COMPLEXES

When heated to 97-degrees-C, the complex Ru4(CO)12[mu-SCH2CMe2CH2]2 (1) was transformed into two new hexaruthenium cluster complexes, Ru6(CO)13(mu3-SCH2CMe2CH2)4 (2) and Ru6(CO)12(mu-SCH2CMe2CH2)(mu3-SCH2CMe2CH2)3[mu3-SCH2C(Me)(CH2)CH2](mu-H) (3), that contain four and five ring-opened 3,3-dimethylthietane (3,3-DMT) ligands, respectively. In compound 3 one of the ring-opened DMT ligands has also undergone a CH activation on one of the methyl groups. Compound 2 reacts with additional 3,3-DMT at 97-degrees-C to form 3 in 18% yield. When treated with CO at 95-degrees-C (500 psi), compound 2 yielded 4,4-dimethylthiobutyrolactone and Ru3(CO)12. It was also found that the complex Os3(CO)11(SCH2CMe2CH2C=O) (4) yields 4,4-dimethylthiobutyrolactone when treated with CO at 120-degrees-C (1200 psi). Crystal data for 2: space group P2(1)/n, a = 22.652 (7) angstrom, b = 11.712 (2) angstrom, c = 19.965 (6) angstrom, beta = 115.75 (2)-degrees, Z = 4, 3665 reflections, R = 0.021. Crystal data for 3: space group P2(1)/c, a = 17.332 (8) angstrom, b = 14.668 (9) angstrom, c = 19.823 (9) angstrom, beta = 91.27 (4)-degrees, Z = 4, 1875 reflections, R = 0.050.