Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai 200433, People's Republic of China.
Inorg Chem. 2010 Mar 15;49(6):2793-8. doi: 10.1021/ic902296d.
Tp(Me2)LnCl(2) (1) reacts with 2 equiv of KN(SiMe(3))(2) in tetrahydrofuran at room temperature to yield the ligand redistribution/gamma-deprotonation products (Tp(Me2))(2)Ln((Me(3)Si)(2)N)(2)Ln(CH(2))SiMe(2)N(SiMe(3)) [Ln = Er (2), Y (3)]. Complex 2 can also be obtained by reacting (Me(3)Si)(2)NErCl with KTp(Me2). However, 1 reacts with 1.5 and 1 equiv of KN(SiMe(3))(2) to yield (Tp(Me2))(2)Er((Me(3)Si)(2)N)(3)ErCl (4) and (Tp(Me2))(2)Er{(Me(3)Si)(2)N)Tp(Me2)ErCl(mu-Cl)(2)K}(-) (5), respectively. Furthermore, it is found that 2 reacts with 2 equiv of CyN=C=NCy (Cy = cyclohexyl) to give the tandem HN(SiMe(3))(2) elimination and Ln-C insertion product (Tp(Me2))Er[(CyN)(2)CCH(2)SiMe(2)N(SiMe(3))] (6) in 71% isolated yield. The results reveal that the gamma-deprotonation degree of advancement increases with an increase of the steric hindrance around the central metal ion. All new complexes have been characterized by elemental analysis and spectroscopic properties, and their solid-state structures have also been determined through single-crystal X-ray diffraction analysis.
(Me2)LnCl(2) (1) 与 2 当量的 KN(SiMe(3))(2) 在四氢呋喃中于室温下反应，生成配体重新分布/γ-去质子化产物(Tp(Me2))(2)Ln((Me(3)Si)(2)N)(2)Ln(CH(2))SiMe(2)N(SiMe(3)) [Ln = Er (2), Y (3)]。复合物 2 也可以通过反应(Me(3)Si)(2)NErCl 与 KTp(Me2)来获得。然而，1 与 1.5 和 1 当量的 KN(SiMe(3))(2)反应，分别生成(Tp(Me2))(2)Er((Me(3)Si)(2)N)(3)ErCl (4)和(Tp(Me2))(2)Er{(Me(3)Si)(2)N)Tp(Me2)ErCl(mu-Cl)(2)K}(-) (5)。此外，发现 2 与 2 当量的 CyN=C=NCy (Cy = 环己基)反应，以 71%的分离产率得到串联的 HN(SiMe(3))(2)消除和 Ln-C 插入产物(Tp(Me2))Er[(CyN)(2)CCH(2)SiMe(2)N(SiMe(3))] (6)。结果表明，γ-去质子化程度的推进随着中心金属离子周围的空间位阻的增加而增加。所有新的配合物都通过元素分析和光谱性质进行了表征，并通过单晶 X 射线衍射分析确定了它们的固态结构。
