Di(indenyl)beryllium
Di(indenyl)beryllium
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二(茚基)铍
DOI：
10.1002/anie.202107980
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Hanusa, Timothy P.
中科院分区：
文献类型：
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作者：
Koby, Ross F.;Schley, Nathan D.;Hanusa, Timothy P.
铍茂[BeCp 2]中的键合花了几十年时间才建立，这是由于其意想不到的混合hapticity结构（即，[Be(η5-Cp）（η1-Cp）]）。含有茚基配体的铍络合物，其是铍阴离子的近亲，但也已知其表现出其自身的键合特性（例如，[001 pdf 1st-31 files]容易的η5位移），仍然未知。它们的合成的标准复分解方法（例如，与K[Ind′] + BeX 2在醚溶剂中反应）产生难处理的油，从中不能分离出任何可鉴定的物质。相比之下，机械化学制备，包括BeBr 2和茚化钾的无溶剂研磨，导致产生离散的（茚基）铍络合物，包括[Be（C9 H7）2]（1）和[Be{1，3-（SiMe 3）2C 9 H5}Br]（2）。前者在固态下显示η5/η1-配位的配体，但DFT计算表明η5/η5-构象的能量高出不到5 kcal mol− 1。
The bonding in beryllocene, [BeCp2], took decades to establish, owing to its unexpected mixed hapticity structure (i.e., [Be(η5‐Cp)(η1‐Cp)]). Beryllium complexes containing the indenyl ligand, which is a close relative of the cyclopentadienyl anion, but which is also known to exhibit its own bonding peculiarities (e.g., facile η5⇄ η3shifts), have remained unknown. Standard metathetical approaches to their synthesis (e.g., with K[Ind′] + BeX2in an ether solvent) give rise to intractable oils from which nothing identifiable can be isolated. In contrast, mechanochemical preparation, involving the solvent‐free grinding of BeBr2and potassium indenides, leads to the production of discrete (indenyl)beryllium complexes, including [Be(C9H7)2] (1) and [Be{1,3‐(SiMe3)2C9H5}Br] (2). The former displays η5/η1‐coordinated ligands in the solid state, but DFT calculations indicate that an η5/η5‐conformation is less than 5 kcal mol−1higher in energy.