Stimuli‐Responsive Frustrated Lewis‐Pair‐Type Reactivity of a Tungsten Iminoazaphosphiridine Complex |
| |
Authors: | José Manuel Villalba Franco Dr Gregor Schnakenburg Prof Dr Takahiro Sasamori Prof Dr Arturo Espinosa Ferao Prof Dr Rainer Streubel |
| |
Institution: | 1. Institut für Anorganische Chemie, Reinischen Friedrich‐Wilhelms‐Universit?t Bonn, Gerhard‐Domagk‐Strasse 1, 53121 Bonn (Germany), Fax:(+49)?228‐739616;2. Institut for Chemical Research, Kyoto University, Gokasho Uji, Kyoto, 611‐0011 (Japan);3. Departamento de Química Orgánica, Universidad de Murcia, Campus de Espinardo, 30100 Murcia (Spain), Fax:(+34)?868‐884149 |
| |
Abstract: | Reactions of 3‐imino‐azaphosphiridine complexes 1 a,b with carbodiimides 2 a,b , isocyanates 3 a,b , and carbon dioxide are described. Whereas exchange of the carbodiimide unit occurs in the first case, an overall ring expansion takes place with phenyl isocyanate ( 3 a ) and carbon dioxide to yield complexes 4 and 5 bearing novel 1,3,5‐oxazaphospholane ligands; the isopropyl derivative 3 b did not react under these conditions. DFT calculations provide insight into the pathway of the reaction with carbon dioxide with model complex 1 c , revealing effects of initial non‐covalent interactions with the substrate onto the ring bonding, thus triggering an initially masked frustrated Lewis‐pair‐type behavior. |
| |
Keywords: | azaphosphiridines carbodiimides carbon dioxide frustrated Lewis pairs phosphorus |
|
|