Phosphetes via Transition Metal Free Ring Closure – Taking the Proper Turn at a Thermodynamic Crossing |
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| Authors: | Fabian Roesler Máté Kovács Dr Clemens Bruhn Dr Zsolt Kelemen Prof Dr Rudolf Pietschnig |
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| Institution: | 1. Institute for Chemistry and CINSaT, University of Kassel, Heinrich Plett-Straße 40, 34132 Kassel, Germany;2. Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szt. Gellért tér 4, H-1111 Budapest, Hungary |
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| Abstract: | 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. |
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| Keywords: | cyclization density functional calculations luminescence phosphorus heterocycles silanes |
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