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通过氧化还原驱动的分子内环化简便合成稳定的侧基磷炔配合物

Facile Synthesis of a Stable Side-on Phosphinyne Complex by Redox Driven Intramolecular Cyclisation.

作者信息

Lange Helge, Schröder Henning, Oberem Elisabeth, Villinger Alexander, Rabeah Jabor, Ludwig Ralf, Neymeyr Klaus, Seidel Wolfram W

机构信息

Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.

Institut für Mathematik, Universität Rostock, Ulmenstraße 69, 18057, Rostock, Germany.

出版信息

Chemistry. 2020 Sep 4;26(50):11492-11502. doi: 10.1002/chem.201905750. Epub 2020 Aug 7.

DOI:10.1002/chem.201905750
PMID:32181544
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7540294/
Abstract

Alkyne complexes with vicinal substitution by a Lewis acid and a Lewis base at the coordinated alkyne are prospective frustrated Lewis pairs exhibiting a particular mutual distance and, hence, a specific activation potential. In this contribution, investigations on the generation of a W alkyne complex bearing a phosphine as Lewis base and a carbenium group as Lewis acid are presented. Independently on potential substrates added, an intramolecular cyclisation product was always isolated. A subsequent deprotonation step led to an unprecedented side-on λ -phosphinyne complex, which is interpreted as highly zwitterionic according to visible absorption spectroscopy supported by TD-DFT. Low-temperature P NMR and EPR spectroscopic measurements combined with time-dependent IR-spectroscopic monitoring provided insights in the mechanism of the cyclisation reaction. Decomposition of the multicomponent IR spectra by multivariate curve resolution and a kinetic hard-modelling approach allowed the derivation of kinetic parameters. Assignment of the individual IR spectra to potential intermediates was provided by DFT calculations.

摘要

在配位炔烃处被路易斯酸和路易斯碱邻位取代的炔烃配合物是具有特定相互距离从而具有特定活化潜力的潜在受阻路易斯对。在本论文中，展示了对带有膦作为路易斯碱和碳正离子基团作为路易斯酸的钨炔烃配合物生成的研究。无论添加何种潜在底物，总是分离得到分子内环化产物。随后的去质子化步骤产生了一种前所未有的侧基λ-磷炔配合物，根据TD-DFT支持的可见吸收光谱，该配合物被解释为高度两性离子。低温磷核磁共振和电子顺磁共振光谱测量结合时间分辨红外光谱监测为环化反应的机理提供了见解。通过多元曲线分辨和动力学硬建模方法对多组分红外光谱进行分解，从而得出动力学参数。通过密度泛函理论计算将各个红外光谱归属到潜在中间体。

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