Organometallics 2013, 32, 2608.
Kun Nie (聂昆), Weikai Gu (顾为凯), Yingming Yao (姚英明),* Yong Zhang (张勇), and Qi Shen (沈琪).
A series of neutral lanthanide complexes supported by ONNO Salalen-type ligands were synthesized, and their catalytic activity for the polymerization of rac-lactide (rac-LA) was explored. The amine elimination reactions of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with the ONNO Salalen-type ligand L1H2 (L1 = (2-O-C6H2-But2-3,5)CH═NCH2CH2N(Me)CH2(2-O-C6H2-But2-3,5)) in a 1:1 molar ratio in tetrahydrofuran (THF) gave the neutral lanthanide amides L1Ln[N(SiMe3)2](THF) (Ln = Y (1), Sm (2), Nd (3)). Reaction of the lanthanide amides with benzyl alcohol produces the dimeric lanthanide alkoxo complex (L1LnOCH2Ph)2 (Ln = Y (4), Sm (5)) in high isolated yield. Y[N(SiMe3)2]3(μ-Cl)Li(THF)3 reacted with the Salalen-type ligand L2H2 (L2 = (2-O-C6H2-But2-3,5)CH═NCH2CH2N(Me)CH2{2-O-C6H2-(CPhMe2)2-3,5}) in a 1:l molar ratio in THF also gave the desired yttrium amide, but this complex could not be separated because of its very good solubility even in n-pentane. The proton exchange reactions of L1H2 and L2H2 with (C5H5)3Ln(THF) in a 1:1 molar ratio in THF and then with 1 equiv of benzyl alcohol gave the desired lanthanide alkoxides [L1Ln(OCH2Ph)]2 (Ln = Y (4), Sm (5), Yb (6)) and [L2Y(OCH2Ph)]2 (7), respectively. Complexes 1–7 were well characterized by elemental analyses, IR spectra, X-ray single-crystal structure determination, and NMR spectroscopy in the case of complexes 1, 4, and 7. Complexes 1–3 are isostructural and have a solvated monomeric structure. The coordination geometry around the lanthanide atom can be best described as a distorted trigonal bipyramid. Complexes 4–7 are dimeric species in the solid state. They all contain a Ln2O2 core bridging through the oxygen atoms of the two OCH2Ph groups. Each of the lanthanide atoms is also six-coordinated to form a distorted octahedron. It was found that all the complexes are efficient initiators for the ring-opening polymerization of rac-LA, giving PLA with good heterotacticity (Pr up to 0.85). The observed order of increase in activity is in agreement with the order of the ionic radii, whereas the stereoselectivity is in reverse order. The steric bulkiness of the substituents on the phenol ring has no obvious impact on the rate and stereocontrolability of the polymerizations. The Ln–O species resulted in more controllable polymerization than the corresponding Ln–N species, and complex 4 can initiate rac-LA polymerization in a controlled manner.
链接：//pubs.acs.org/doi/abs/10.1021/om4001023
