Jiang Wen, Rajeshkumar Thayalan, Guo Mengyue, Lin Yuejian, Maron Laurent, Zhang Lixin
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University 2005 Songhu Road, Jiangwan Campus Shanghai 200438 P. R. China
LPCNO, Université de Toulouse 31077 Toulouse France
Chem Sci. 2024 Jan 31;15(10):3495-3501. doi: 10.1039/d3sc06599e. eCollection 2024 Mar 6.
Guanidinate homometallic rare-earth ethyl complexes [LLn(-:-Et)(Et)] (Ln = Y(1-Y), Lu(1-Lu)) and heterobimetallic rare-earth ethyl complexes LLn(Et)(-:-Et)(--Et)(AlEt) (Ln = Y(2-Y), Lu(2-Lu)) have been synthesized by the treatment of LLn(CHCHNMe-) (L = (PhCH)NC(NCHPr-2,6)) with different equivalents of AlEt in toluene at ambient temperature. Interestingly, the unprecedented rare-earth ethyne complex LY(--Et)(AlEt) (3-Y) containing a [CH] unit was afforded from 2-Y. The formation mechanism study on 3-Y was carried out by DFT calculations. Furthermore, the nature of the bonding of 3-Y was also revealed by NBO analysis. The reactions of LLn(CH CHNMe-) (Ln = Y, Lu) with AlEt (4 equiv.) in toluene at 50 °C produced firstly the non-Cp rare-earth ethylene complex LY(-::-CH)[(--Et)(AlEt)(--Et)(AlEt)] (4-Y), and the Y/Al ethyl complex LY[(--Et)(AlEt)] (5-Y) as an intermediate of 4-Y was isolated from the reaction of LY(CHCHNMe-) with AlEt (4 equiv.) in toluene at -10 °C.
通过在室温下将LLn(CHCHNMe-)（L = (PhCH)NC(NCHPr-2,6)）与不同当量的AlEt在甲苯中反应，合成了胍基金属稀土乙基配合物[LLn(-:-Et)(Et)]（Ln = Y(1-Y)，Lu(1-Lu)）和异双金属稀土乙基配合物LLn(Et)(-:-Et)(--Et)(AlEt)（Ln = Y(2-Y)，Lu(2-Lu)）。有趣的是，从2-Y得到了含有[CH]单元的前所未有的稀土乙炔配合物LY(--Et)(AlEt)（3-Y）。通过密度泛函理论（DFT）计算对化合物3-Y进行了生成机理研究。此外，自然键轨道（NBO）分析也揭示了3-Y的成键本质。LLn(CH CHNMe-)（Ln = Y，Lu）与AlEt（4当量）在50℃下于甲苯中反应，首先生成非茂稀土乙烯配合物LY(-::-CH)[(--Et)(AlEt)(--Et)(AlEt)]（4-Y），并且从LY(CHCHNMe-)与AlEt（4当量）在-10℃下于甲苯中的反应中分离出作为4-Y中间体的Y/Al乙基配合物LY[(--Et)(AlEt)]（5-Y）。
