Lindl Felix, Fantuzzi Felipe, Mailänder Lisa, Hörl Christian, Bélanger-Chabot Guillaume, Braunschweig Holger
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Chem Commun (Camb). 2022 Apr 12;58(30):4735-4738. doi: 10.1039/d2cc00543c.
Boroles are well known to undergo ring expansion reactions with organic azides to yield 1,2-azaborinines. A synthon featuring both azide and borole moieties within the same molecule, 1-azido-2,3,4,5-tetraphenylborole, was found to be much less stable than the related, previously-reported azidoborafluorene and decomposed to intractable mixtures well below room temperature. It could, however, be trapped at -75 °C through the formation of Lewis base adducts, even in the form of the "azide-stabilized azidoborole" complex anion diazidoborolate. DFT calculations provide a rationale for the low stability of the azidoborole under study.
众所周知，硼杂环戊二烯会与有机叠氮化物发生扩环反应生成1,2 - 氮杂硼杂苯。在同一分子中同时具有叠氮基和硼杂环戊二烯部分的合成子1 - 叠氮基 - 2,3,4,5 - 四苯基硼杂环戊二烯，被发现比相关的、先前报道的叠氮基硼芴稳定性差得多，并且在远低于室温的温度下就分解为难以处理的混合物。然而，即使以“叠氮基稳定的叠氮基硼杂环戊二烯”配合物阴离子重氮硼酸根离子的形式，它也可以在 - 75°C下通过形成路易斯碱加合物而被捕获。密度泛函理论计算为所研究的叠氮基硼杂环戊二烯的低稳定性提供了一个理论依据。
