Alkane elimination reactions of amino-amino-bis(phenols) H 2 L 1-4 , Salan H 2 L 5 , and methoxy--diimines HL 6,7 with lanthanide tris(alkyl)s, Ln(CH 2 SiMe 3 ) 3 (THF) 2 (Ln ) Y, Lu), respectively, afforded a series of lanthanide alkyl complexes 1-8 with the release of tetramethylsilane. Complexes 1-6 are THFsolvated mono(alkyl)s stabilized by O,N,N,O-tetradentate ligands. Complexes 1-3 and 5 adopt twisted octahedral geometry, whereas 4 contains a tetragonal bipyramidal core. Bearing a monoanionic moiety L 6 (L 7 ), complex 7 (8) is a THF-free bis(alkyl). In complex 7, the O,N,N-tridentate ligand combined with two alkyl species forms a tetrahedral coordination core. Complexes 1, 2, and 3 displayed modest activity but high stereoselectivity for the polymerization of rac-lactide to give heterotactic polylactide with the racemic enchainment of monomer units P r ranging from 0.95 to 0.99, the highest value reached to date. Complex 5 exhibited almost the same level of activity albeit with relatively low selectivity. In contrast, dramatic decreases in activity and stereoselectivity were found for complex 4. The Salan yttrium alkyl complex 6 was active but nonselective. Bis(alkyl) complexes 7 and 8 were more active than 1-3 toward polymerization of rac-LA, however, to afford atactic polylactides due to di-active sites. The ligand framework, especially the "bridge" between the two nitrogen atoms, played a significant role in governing the selectivity of the corresponding complexes via changing the geometry of the metal center. The NMR spectrum of the active species of the rac-lactide oligomer attached to complex 1 demonstrated a coordination-insertion mechanism. In addition it also confirmed that the geometry of the metal center of complex 1 in the solid state was retained in solution (THF) during the polymerization, which contributed significantly to the high selectivity of the complex.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.