Rare earth metal bis(alkyl) complexes bearing amino phosphine ligands: Synthesis and catalytic activity toward ethylene polymerization |
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| Authors: | Shihui Li Wei Miao Tao Tang Xuesi Chen |
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| Institution: | a State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b Graduate School of the Chinese Academy of Sciences, Beijing 100039, China |
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| Abstract: | Reactions of neutral amino phosphine compounds HL1-3 with rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2, afforded a new family of organolanthanide complexes, the molecular structures of which are strongly dependent on the ligand framework. Alkane elimination reactions between 2-(CH3NH)-C6H4P(Ph)2 (HL1) and Lu(CH2SiMe3)3(THF)2 at room temperature for 3 h generated mono(alkyl) complex (L1)2Lu(CH2SiMe3)(THF) (1). Similarly, treatment of 2-(C6H5CH2NH)-C6H4P(Ph)2 (HL2) with Lu(CH2SiMe3)3(THF)2 afforded (L2)2Lu(CH2SiMe3)(THF) (2), selectively, which gradually deproportionated to a homoleptic complex (L2)3Lu (3) at room temperature within a week. Strikingly, under the same condition, 2-(2,6-Me2C6H3NH)-C6H4P(Ph)2 (HL3) swiftly reacted with Ln(CH2SiMe3)3(THF)2 at room temperature for 3 h to yield the corresponding lanthanide bis(alkyl) complexes L3Ln(CH2SiMe3)2(THF)n (4a: Ln = Y, n = 2; 4b: Ln = Sc, n = 1; 4c: Ln = Lu, n = 1; 4d: Ln = Yb, n = 1; 4e: Ln = Tm, n = 1) in high yields. All complexes have been well defined and the molecular structures of complexes 1, 2, 3 and 4b-e were confirmed by X-ray diffraction analysis. The scandium bis(alkyl) complex activated by AlEt3 and Ph3C]B(C6F5)4], was able to catalyze the polymerization of ethylene to afford linear polyethylene. |
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| Keywords: | Lanthanide Alkyl complex Ethylene Polymerization Phosphine |
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