Ring opening and carbonylation of 3,3-dimethylthietane ligands in ruthenium carbonyl cluster complexes

Article abstract of DOI:10.1021/om00046a048

When heated to 97°C, the complex Ru₄(CO)₁₂[μ-SCH₂CMe₂CH ₂]₂ (1) was transformed into two new hexaruthenium cluster complexes, Ru₆(CO)₁₃(μ₃-SCH₂CMe ₂CH₂)₄ (2) and Ru₆(CO)₁₂(μ-SCH₂CMe₂CH ₂)(μ₃-SCH₂CMe₂CH ₂)₃[μ₃-SCH₂C(Me)(CH ₂)CH₂](μ-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°C to form 3 in 18% yield. When treated with CO at 95°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°C (1200 psi). Crystal data for 2: space group P2₁/n, a = 22.652 (7) A?, b = 11.712 (2) A?, c = 19.965 (6) A?, β = 115.75 (2)°, Z = 4, 3665 reflections, R = 0.021. Crystal data for 3: space group P2₁/c, a = 17.332 (8) A?, b = 14.668 (9) A?, c = 19.823 (9) A?, β = 91.27 (4)°, Z = 4, 1875 reflections, R = 0.050.