Laboratory of Functionalized Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, China.
Inorg Chem. 2013 Jun 3;52(11):6417-26. doi: 10.1021/ic4003109. Epub 2013 May 22.
The reactions of Me2Si(C9H6CH2CH2-DG)2 (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N(CH2CH2)2O (4)) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 in toluene afforded a series of racemic divalent rare-earth metal complexes: {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2-DG)2}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = Yb (11) and Eu (12); DG = N(CH2CH2)2O, RE = Yb (13) and Eu (14)). Similarly, the racemic divalent rare-earth metal complexes {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H5CH2CH2OMe)2Li2 with NdCl3 gave a racemic dimeric neodymium chloride {η(5):η(1):η(5)-Me2Si(C9H5CH2CH2OMe)2NdCl}2 (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)2Li2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(μ-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond α-adjacent to the nitrogen atom. Complexes 19 and {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)2Li2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms.
反应 Me2Si(C9H6CH2CH2-DG)2(DG = NMe2(1)、CH2NMe2(2)、OMe(3)和 N(CH2CH2)2O(4))与[(Me3Si)2N]3RE(μ-Cl)Li(THF)3 在甲苯中得到一系列外消旋的二价稀土金属配合物：{η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2-DG)2}RE(DG = NMe2,RE = Yb(6)和 Eu(7);DG = CH2NMe2,RE = Yb(8)、Eu(9)和 Sm(10);DG = OMe,RE = Yb(11)和 Eu(12);DG = N(CH2CH2)2O,RE = Yb(13)和 Eu(14))。同样，也得到了外消旋的二价稀土金属配合物{η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE(RE = Yb(15)和 Eu(16))。Me2Si(C9H5CH2CH2OMe)2Li2与 NdCl3的反应得到了外消旋的二聚钕氯化物{η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2OMe)2NdCl}2(17)，而 Me2Si(C9H5CH2CH2NMe2)2Li2与 SmCl3的反应则得到了桥连氯化锂的外消旋二核钐氯化物{η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(μ-LiCl)(18)。复合物 18 与 LiCH2SiMe3 的进一步反应通过活化氮原子相邻的 sp(3)C-H 键，提供了一个意想不到的稀土金属烷基配合物{η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm(19)。复合物 19 和{η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y(20)也可以通过 Me2Si(C9H5CH2CH2NMe2)2Li2 与 RECl3 的一锅法反应，然后用 LiCH2SiMe3 处理得到。所有化合物均通过光谱方法和元素分析进行了充分的表征。复合物 6-10 和 14-20 还通过单晶 X 射线衍射分析进行了进一步的表征。所有制备的稀土金属配合物均为外消旋，表明通过桥联和供体原子的分子内配位之间的协同作用，可以可控地合成外消旋有机稀土金属配合物。
