Feng Zhijun, Wei Yun, Zhou Shuangliu, Zhang Guangchao, Zhu Xiancui, Guo Liping, Wang Shaowu, Mu Xiaolong
Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials, School of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, P. R. China.
Dalton Trans. 2015 Dec 21;44(47):20502-13. doi: 10.1039/c5dt03214h. Epub 2015 Nov 9.
The reactivity of several functionalized indoles 2-(RNHCH2)C8H5NH (R = C6H5 (1), (t)Bu (2), 2,6-(i)Pr2C6H3 (3)) with rare-earth metal amides is described. Reactions of 1 or 2 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 (RE = Eu, Yb) respectively produced the europium complexes [2-(C6H5N[double bond, length as m-dash]CH)C8H5N]2Eu[N(SiMe3)2] (4) and [2-((t)BuN[double bond, length as m-dash]CH)C8H5N]Eu[N(SiMe3)2]2 (5), and the ytterbium complex [2-((t)BuN[double bond, length as m-dash]CH)C8H5N]2Yb[N(SiMe3)2] (6), containing bidentate anionic indolyl ligands via dehydrogenation of the amine to the imine. In contrast, reactions of the more sterically bulky indole 3 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 afforded complexes [2-(2,6-(i)Pr2C6H3NCH2)C8H5N]REN(SiMe3)22 (RE = Yb (7), Y (8), Er (9), Dy (10)) with the deprotonated indolyl ligand. While reactions of 3 with yttrium and ytterbium amides in refluxing toluene respectively gave the complexes [2-(2,6-(i)Pr2C6H3N[double bond, length as m-dash]CH)C8H5N]3Y (11) and [2-(2,6-(i)Pr2C6H3N[double bond, length as m-dash]CH)C8H5N]2Yb(II)(THF)2 (12), along with transformation of the amino group to the imino group, and also with a reduction of Yb(3+) to Yb(2+) in the formation of 12. Reactions of 3 with samarium and neodymium amides provided novel dinuclear complexes {[μ-η(5):η(1):η(1)-2-(2,6-(i)Pr2C6H3NCH2)C8H5N]RE[N(SiMe3)2]}2 (RE = Sm (13), Nd (14)) having indolyl ligands in μ-η(5):η(1):η(1) hapticities. The pathway for the transformation of the amino group to the imino group is proposed on the basis of the experimental results. The new complexes displayed excellent activity in the intramolecular hydroamination of aminoalkenes.
描述了几种官能化吲哚2-(RNHCH2)C8H5NH（R = C6H5 (1)、(t)Bu (2)、2,6-(i)Pr2C6H3 (3)）与稀土金属酰胺的反应活性。1或2与[(Me3Si)2N]3RE(μ-Cl)Li(THF)3（RE = Eu、Yb）反应分别生成铕配合物[2-(C6H5N═CH)C8H5N]2Eu[N(SiMe3)2] (4)和[2-((t)BuN═CH)C8H5N]Eu[N(SiMe3)2]2 (5)，以及镱配合物[2-((t)BuN═CH)C8H5N]2Yb[N(SiMe3)2] (6)，这些配合物通过胺脱氢生成亚胺含有双齿阴离子吲哚基配体。相比之下，空间位阻更大的吲哚3与[(Me3Si)2N]3RE(μ-Cl)Li(THF)3反应得到配合物[2-(2,6-(i)Pr2C6H3NCH2)C8H5N]REN(SiMe3)22（RE = Yb (7)、Y (8)、Er (9)、Dy (10)），带有去质子化的吲哚基配体。而3与钇和镱酰胺在回流甲苯中反应分别得到配合物[2-(2,6-(i)Pr2C6H3N═CH)C8H5N]3Y (11)和[2-(2,6-(i)Pr2C6H3N═CH)C8H5N]2Yb(II)(THF)2 (12)，同时氨基转化为亚氨基，并且在形成12的过程中Yb(3+)还原为Yb(2+)。3与钐和钕酰胺反应提供了新型双核配合物{[μ-η(5):η(1):η(1)-2-(2,6-(i)Pr2C6H3NCH2)C8H5N]RE[N(SiMe3)2]}2（RE = Sm (13)、Nd (14)），其吲哚基配体具有μ-η(5):η(1):η(1)的配位模式。根据实验结果提出了氨基转化为亚氨基的途径。这些新配合物在氨基烯烃的分子内氢胺化反应中表现出优异的活性。
