The catalytic ring-opening cyclooligomerization (ROC) of thietane by the complexes M(CO)(5)L (M=Cr and W; L=CO, thietane and 1,5,9-trithiacyclododecane)

The following four compounds have been synthesized: M(CO)(5)L (3 and 4, where M = Cr and W, and L = SCH2CH2CH2), W(CO)(5)(12S3) (5, where 12S3 = 1,5,9-trithiacyclododecane), and [W(CO)(5)](2)(12S3) (6). The molecular structures of 4 and 5 were established by single-crystal Xray diffraction analyses. Both compounds contain a W(CO)(5) group coordinated to one of the sulfur atoms of the heterocycle. 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 = P2(1)2(1)2(1), a = 12.906(2) Angstrom, b = 13.730(4) Angstrom, c = 6.427(1) Angstrom, Z = 4, 1306 reflections, R = 0.033; for 5: space group = P (1) over bar, a = 12.703(1) Angstrom, b = 13.510(2) Angstrom, c = 5.833(1) Angstrom, alpha = 101.75(1)degrees, beta = 97.54(1)degrees, gamma = 101.70(1)degrees, Z = 2, 2225 reflections, R = 0.023.