Protonolysis reactions of [(Me3Si)2N]3Ln(µ-Cl)Li(THF)3 (Ln = Pr; Nd; Sm; Eu) with three equiv. of 4,6-dimethylpyrimidine-2-thiol (dmpymtH) gave rise to four Ln(III) pyrimidine-2-thionate complexes Li[Ln(dmpymt)4] (Ln = Pr (1); Ln = Nd (2); Ln = Sm (3); Ln = Eu (4)). Complexes 1-4 displayed excellent catalytic performances on cyclodimerization of isocyanates to produce substituted ureas via elimination of CO, which represents the first example of lanthanide thiolates exhibiting a high catalytic activity and a high selectivity on cyclodimerization of isocyanates.
H. �X. Li, M. �L. Chen, H. �M. Wang, X. �J. Yang, Z. �G. Ren, J. �P. Lang*,