分子间 η2 - 和 κ2 - 复合物:合成,结合和易于相互转换
Mikhail A Bogachev1, Alexander N Selikhov1,2, Anton V Cherkasov1
1Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, GSP-445, Nizhny Novgorod 603950, Russia.
这项研究详细介绍了-和-复合物的合成. 这些复合物存在于平衡状态,随着或度的转移而易于相互转换.
科学领域:
- 有机金属化学
- 主要组化学
- 计算化学
背景情况:
- 含有不和碳化合物的复合物是有机合成中的关键中间体.
- 了解配体相互作用的性质对于催化剂设计至关重要.
研究的目的:
- 开发一个合成路径 η2-复合物.
- 用量子化学方法研究和的相互作用.
- 探索这些复合物的反应性和平衡力学.
主要方法:
- 使用大型碳联体合成e2-复合物.
- 复合物的与和的反应.
- 分子中的原子量子理论 (QTAIM) 分析.
- 局部对自然轨道结合集群的糖尿病化与单个,双重和扰乱三重 (DLPNO-CCSD) 计算.
主要成果:
- 成功合成了 η2-基复合物和双核μ-η2:η2-复合物.
- 通过QTAIM进行静电Li-相互作用的表征.
- 证明可逆的基-基配体交换,形成具有基互动的基复合物.
- 相互作用能量和分散贡献的量化,揭示了Li-alkene和Li-alkane复合体之间的小能量差异.
- -和-复合物的转化为二复合物.
结论:
- 为 η2-基复合物建立了一种多功能合成方法.
- 证实了基结合的静电性质.
- 在-和-复合物之间存在动态平衡,可通过反应剂度调节.
- 这项研究提供了有关有机化合物的结合和反应性的基本见解.
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