Abstract
ABSTRACTReaction of LnCl3 first with three equivalent of C5H5Na in THF, then with one equivalent of benzyl mercaptan, led to complexes of [(C5H5)2Ln(SCH2Ph)]2 (Ln = Sm(1), Yb(2)), being characterized by infrared spectra, elemental analyses and X-ray crystallography for 2. Complex 2 is a dimer with two thiolate ligands as bridging groups in eight coordinate. The Yb-S(benzyl) bonds in 2 (2.703(19) and 2.719(2) Å, respectively) were longer than the Yb-S(aryl) bonds (about 2.640 Å) in analogous complexes. The catalytic property for the polymerization of ε-caprolactone by 1 and 2 was studied. Similar experiment was also made with [(C5H5)2Ln(SPh-p-CH3)(THF)]2 (Ln = Sm(3), Yb(4)) for comparison. It was found that complex 2 showed the activity best, and the activity decreased in the order of 2 > 3 > 1 > 4. When [ε-CL]0/[Ln] was 500 and the polymerization temperature was 35°C, complex 2 catalyzed the polymerization in living character, which could not be achieved by lanthanide arylthiolates such as 3 and 4.
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