Wang Long, Dong Shunxi, Daniliuc Constantin G, Liu Lei, Grimme Stefan, Knitsch Robert, Eckert Hellmut, Hansen Michael Ryan, Kehr Gerald, Erker Gerhard
Organisch-Chemisches Institut , Westfälische Wilhelms-Universität Münster , Corrensstr. 40 , 48149 Münster , Germany . Email:
Mulliken Center for Theoretical Chemistry , Institut für Physikalische und Theoretische Chemie , Universität Bonn , Beringstr. 4 , 53115 Bonn , Germany.
Chem Sci. 2017 Dec 14;9(6):1544-1550. doi: 10.1039/c7sc04394e. eCollection 2018 Feb 14.
The trifunctional P/B/B frustrated Lewis pairs featuring bulky aryl groups at phosphorus [Dmesp (), Tipp (), Mes* ()] react with H by heterolytic hydrogen splitting followed by cleavage of HB(CF) to give the zwitterionic six-membered heterocyclic PH phosphonium/borate products . Compounds react with carbon monoxide by means of a Lewis acid induced CO insertion/rearrangement sequence that eventually results in the formation of the macrocyclic dimers . The respective carbonylation reaction of the Mes*P/B/B FLP gives the macrocyclic trimer . The new products were characterized spectroscopically and by X-ray diffraction and the reaction mechanism was analyzed by DFT calculations.
在磷原子上带有庞大芳基的三官能团P/B/B受阻路易斯酸碱对[Dmesp（）、Tipp（）、Mes*（）]通过异裂氢分裂与H反应，随后HB（CF）裂解，生成两性离子六元杂环PH鏻/硼酸盐产物。化合物通过路易斯酸诱导的CO插入/重排序列与一氧化碳反应，最终形成大环二聚体。Mes*P/B/B FLP的相应羰基化反应生成大环三聚体。通过光谱和X射线衍射对新产物进行了表征，并通过DFT计算分析了反应机理。
