Schumann André, Reiß Fabian, Jiao Haijun, Rabeah Jabor, Siewert Jan-Erik, Krummenacher Ivo, Braunschweig Holger, Hering-Junghans Christian
Leibniz-Institut für Katalyse e.V. an der Universität Rostock , Albert-Einstein-Straße 29a , 18059 Rostock , Germany . Email:
Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany.
Chem Sci. 2019 Jul 30;10(34):7859-7867. doi: 10.1039/c9sc02322d. eCollection 2019 Sep 14.
Triphosphiranes are three-membered phosphorus cycles and their fundamental reactivity has been studied in recent decades. We recently developed a high-yielding, selective synthesis for various aryl-substituted triphosphiranes. Variation of the reaction conditions in combination with theoretical studies helped to rationalize the formation of these homoleptic phosphorus ring systems and highly reactive intermediates could be isolated. In addition we showed that a titanocene synthon [CpTi(btmsa)] facilitates the selective conversion of these triphosphiranes into titanocene diphosphene complexes. This unexpected reactivity mode was further studied theoretically and experimental evidence is presented for the proposed reaction mechanism.
环三磷烷是三元磷环，近几十年来人们对其基本反应活性进行了研究。我们最近开发了一种高产率、选择性合成各种芳基取代环三磷烷的方法。反应条件的变化与理论研究相结合，有助于解释这些纯磷环体系的形成，并且可以分离出高活性中间体。此外，我们还表明二茂钛合成子[CpTi(btmsa)]能促进这些环三磷烷选择性转化为二茂钛二磷烯配合物。对这种意外的反应模式进行了进一步的理论研究，并为所提出的反应机理提供了实验证据。
