Roesler Fabian, Kovács Máté, Bruhn Clemens, Kelemen Zsolt, Pietschnig Rudolf
Institute for Chemistry and CINSaT, University of Kassel, Heinrich Plett-Straße 40, 34132, Kassel, Germany.
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szt. Gellért tér 4, H-1111, Budapest, Hungary.
Chemistry. 2021 Jul 7;27(38):9782-9790. doi: 10.1002/chem.202101298. Epub 2021 Jun 2.
A transition metal free route to phosphetes featuring an exocyclic alkene unit is presented. In this approach phosphanides are added to a variety of diynes generating phosphaallylic intermediates which depending on the reaction conditions transform either to phosphetes or the corresponding phospholes. Investigation of the reaction mechanism by combined quantum chemical and experimental means identifies phosphole formation as thermodynamically controlled reaction path, whereas kinetic control furnishes the corresponding phosphetes. Structural and luminescence properties of the rare class of phosphetes are explored, as well as for selected key intermediates.
本文介绍了一种无过渡金属合成具有环外烯烃单元的磷杂环丁二烯的方法。在该方法中，磷化物被添加到各种二炔中，生成磷杂烯丙基中间体，根据反应条件，该中间体可转化为磷杂环丁二烯或相应的磷杂环戊二烯。通过量子化学和实验相结合的方法对反应机理进行研究，确定磷杂环戊二烯的形成是热力学控制的反应路径，而动力学控制则产生相应的磷杂环丁二烯。本文还探索了这类罕见的磷杂环丁二烯以及选定的关键中间体的结构和发光性质。
