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Synthesis, structure, and catalytic activity of organolanthanides with chiral biphenyl-based tridentate amidate ligands
- Source :
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Journal of Organometallic Chemistry . May2011, Vol. 696 Issue 10, p2186-2192. 7p. - Publication Year :
- 2011
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Abstract
- Abstract: 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 C 2-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 C 1-symmetric bis-ligated amidate complexes [(κO:κN-1)(σOMe:κO:κN-1)]LnN(SiMe3)2 (Ln = Y (4), Yb (5) and the C 1-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. [Copyright &y& Elsevier]
Details
- Language :
- English
- ISSN :
- 0022328X
- Volume :
- 696
- Issue :
- 10
- Database :
- Academic Search Index
- Journal :
- Journal of Organometallic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 60163042
- Full Text :
- https://doi.org/10.1016/j.jorganchem.2010.11.032