Guo Liping, Zhu Xiancui, Zhang Guangchao, Wei Yun, Ning Lixin, Zhou Shuangliu, Feng Zhijun, Wang Shaowu, Mu Xiaolong, Chen Jun, Jiang Yuzhe
§State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China.
Inorg Chem. 2015 Jun 15;54(12):5725-31. doi: 10.1021/acs.inorgchem.5b00308. Epub 2015 May 21.
A series of N-protected 3-imino-functionalized indolyl ligands 1-R-3-(R'N═CH)C8H5N [R = Bn, R' = 2,6-(i)Pr2C6H3 (HL(1)); R = CH3, R' = 2,6-(i)Pr2C6H3 (HL(2)); R = Bn, R' = (t)Bu (HL(3))] and 1-CH3-2-(2,6-(i)Pr2C6H3N═CH)C8H5N (HL(4)) was prepared via reactions of N-protected indolyl aldehydes with corresponding amines. The C-H σ-bond metathesis followed by alkane elimination reactions between RE(CH2SiMe3)3(thf)2 and HL(1)-HL(3) afforded the carbon σ-bonded indolyl-ligated rare-earth metal monoalkyl complexes. Reactions of RE(CH2SiMe3)3(thf)2 with 2 equiv of HL(1) or HL(2) gave the carbon σ-bonded indolyl-ligated rare-earth metal monoalkyl complexes L(1)2RECH2SiMe3 (RE = Y(1), Er(2), Dy(3)) and L(2)2RECH2SiMe3 (RE = Y(5), Er(6), Dy(7), Yb(8)), while reaction of Yb(CH2SiMe3)3(thf)2 with 2 equiv of HL(1) afforded the ytterbium dialkyl complex L(1)Yb(CH2SiMe3)2(thf)2 (4). Reactions of RE(CH2SiMe3)3(thf)2 with HL(3) gave the tris(heteroaryl) rare-earth metal complexes L(3)3RE (RE = Y(9), Er(10)). In the presence of cocatalysts, the rare-earth metal monoalkyl complexes initiated isoprene polymerization with a high activity (90% conversion of 1000 equiv of isoprene in 25 min) producing polymers with high regio- and stereoselectivity (1,4-cis polymers up to 99%).
通过N-保护的吲哚醛与相应胺的反应，制备了一系列N-保护的3-亚氨基官能化吲哚基配体1-R-3-(R'N═CH)C8H5N [R = Bn，R' = 2,6-(异丙基)2C6H3 (HL(1))；R = CH3，R' = 2,6-(异丙基)2C6H3 (HL(2))；R = Bn，R' = (叔丁基) (HL(3))] 和1-CH3-2-(2,6-(异丙基)2C6H3N═CH)C8H5N (HL(4))。RE(CH2SiMe3)3(thf)2与HL(1)-HL(3)之间发生C-H σ键复分解反应，随后发生烷烃消除反应，得到碳σ键连接的吲哚基配位稀土金属单烷基配合物。RE(CH2SiMe3)3(thf)2与2当量的HL(1)或HL(2)反应，得到碳σ键连接的吲哚基配位稀土金属单烷基配合物L(1)2RECH2SiMe3 (RE = Y(1)，Er(2)，Dy(3)) 和L(2)2RECH2SiMe3 (RE = Y(5)，Er(6)，Dy(7)，Yb(8))，而Yb(CH2SiMe3)3(thf)2与2当量的HL(1)反应，得到镱二烷基配合物L(1)Yb(CH2SiMe3)2(thf)2 (4)。RE(CH2SiMe3)3(thf)2与HL(3)反应，得到三(杂芳基)稀土金属配合物L(3)3RE (RE = Y(9)，Er(10))。在助催化剂存在下，稀土金属单烷基配合物引发异戊二烯聚合反应，活性较高(25分钟内1000当量异戊二烯转化率达90%)，生成具有高区域和立体选择性的聚合物(1,4-顺式聚合物含量高达99%)。
