Synthesis, structure, and catalytic activity of organolanthanides with chiral biphenyl-based tridentate amidate ligands
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- 作者：Qiuwen Wanga ; Furen Zhanga ; Haibin Songb ; Guofu Zia ; gzi@bnu.edu.cn
- 关键词：Chiral amidate ligands ; Organolanthanide complexes ; Asymmetric hydroamination/cyclization ; Polymerization of lactide
- 刊名：Journal of Organometallic Chemistry
- 出版年：2011
- 出版时间：15 May 2011
- 年：2011
- 卷：696
- 期：10
- 页码：2186-2192
- 全文大小：831 K
文摘
Four new chiral organolanthanide amidate complexes have been readily prepared in good yields via silylamine elimination reaction between Ln[N(SiMe3)2]3 (Ln = Sm, Y, Yb) and chiral amidate ligands, (R)-2-(mesitoylamino)-2′-methoxy-6,6′-dimethyl-1,1′-biphenyl (1H) and (R)-2-(mesitoylamino)-2′-dimethylamino-6,6′-dimethyl-1,1′-biphenyl (2H). The steric effect of the ligand coupled with the size effect of the lanthanide ion plays an important role in complex formation. For example, treatment of 1H with half equiv of Sm[N(SiMe3)2]3 gives the C2-symmetric bis-ligated amidate complex (σOMe:κO:κN-1)2SmN(SiMe3)2 (3) in 75 % yield, while reaction of 1H or 2H with half equiv of Ln[N(SiMe3)2]3 (Ln = Y, Yb) affords the C1-symmetric bis-ligated amidate complexes [(κO:κN-1)(σOMe:κO:κN-1)]LnN(SiMe3)2 (Ln = Y (4), Yb (5) and the C1-symmetric mono-ligated amidate complex (σNMe2:κO:κN-2)Y[N(SiMe3)2]2 (6), respectively, in good yields. These organolanthanide amidate complexes have been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analyses. They are active catalysts for asymmetric hydroamination/cyclization of aminoalkenes and ring-opening polymerization of rac-lactide, affording cyclic amines in excellent conversions with good ee values and isotactic-rich polylactides, respectively.