Bis(η6-benzene)lithium Cation, a Fundamental Main Group Organometallic Species.
Bis(η6-benzene)lithium Cation, a Fundamental Main Group Organometallic Species.
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双(δ6-苯)锂阳离子，一种基本的主族有机金属物种
DOI：
10.1002/anie.202108376
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发表时间：
2021
影响因子：
--
通讯作者：
G. Erker
中科院分区：
文献类型：
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作者：
X. Jie;C. G. Daniliuc;A.-L. Wübker;M. R. Hansen;H. Eckert;C. Mück-Lichtenfeld;G. Kehr;G. Erker
报道了最轻金属苯茂金属双(η6-苯)锂阳离子的合成和表征。硼化合物FmesBCl2[Fmes: 2,4,6-三(三氟甲基)苯基]与三摩尔当量的锂硫乙炔试剂Li-C≡C-Fmxyl [Fmxyl: 3,5-双(三氟甲基)苯基]反应。随后从苯中结晶得到[双(η6-苯)Li]+阳离子和[{FmesB(-C≡C-Fmxyl)3}2Li]-阴离子。该母体 [(芳烃)2Li]+ 阳离子在中心锂阳离子处显示一对苯配体的重叠排列，具有均匀的碳-锂键长。类似地制备了相应的含[(η6-甲苯)2Li]+和[(η6-杜烯)2Li]+的盐。双(芳烃)锂阳离子通过X射线衍射、固态7Li MAS NMR光谱进行表征，并通过DFT计算分析它们的键合特征。
The synthesis and characterization of the bis(η6‐benzene)lithium cation, the benzene metallocene of the lightest metal, is reported. The boron compound FmesBCl2[Fmes: 2,4,6‐tris(trifluoromethyl)phenyl] reacted with three molar equivalents of the lithio‐acetylene reagent Li‐C≡C‐Fmxyl [Fmxyl: 3,5‐bis(trifluoromethyl)phenyl]. Subsequent crystallization from benzene gave the [bis(η6‐benzene)Li]+cation with the [{FmesB(‐C≡C‐Fmxyl)3}2Li]−anion. This parent [(arene)2Li]+cation shows an eclipsed arrangement of the pair of benzene ligands at the central lithium cation with uniform carbon‐lithium bond lengths. The corresponding [(η6‐toluene)2Li]+and [(η6‐durene)2Li]+containing salts were similarly prepared. The bis(arene)lithium cations were characterized by X‐ray diffraction, by solid‐state7Li MAS NMR spectroscopy and their bonding features were analyzed by DFT calculations.