The Catalytic Ring‐opening Cyclooligomerization (ROC) of Thietane by the Complexes M(CO)5L (M Cr and W; L = CO, thietane and 1,5,9‐Trithiacyclododecane)

The following four compounds have been synthesized: M(CO)5L (3 and 4, where M = Cr and W, and L = H2), W(CO)5(12S3) (5, where 12S3 = 1,5,9‐trithia‐cyclododecane), and [W(CO)5]2(12S3) (6). The molecular structures of 4 and 5 were established by single‐crystal X‐ray diffraction analyses. Both compounds contain a W(CO)5 group coordinated to one of the sulfur atoms of the hetero‐cycle. The ability of the compounds M(CO)6, 1 and 2 (M = Cr and W), and 3 – 5 to catalytically produce ring opening cyclooligomerization (ROC) of thietane into 12S3 and 24S6, (24S6 = 1,5,9,13,17,21‐hexathiacyclotetracosane) has been investigated. Compounds 1 – 3 have relatively low activity. Compounds 4 and 5 have the highest activity and selectivity for 12S3 formation. Crystal Data for 4: space group = P212121, a = 12.906(2) Å, b = 13.730(4) Å, c = 6.427(1) Å, Z = 4, 1306 reflections, R = 0.033; for 5: space group = P1¯, a = 12.703(1) Å, b = 13.510(2) Å, c = 5.833(1) Å, α = 101.75(1)°, β = 97.54(1)°, γ = 101.70(1)°, Z = 2, 2225 reflections, R = 0.023.