A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non‐covalent Interactions |
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Authors: | Dr Vitaly Nesterov Dr Arturo Espinosa Dr Gregor Schnakenburg Prof?Dr Rainer Streubel |
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Institution: | 1. Institut für Anorganische Chemie der Rheinischen Friedrich‐Wilhelms‐Universit?t Bonn, Gerhard‐Domagk‐Strasse 1, 53121 Bonn (Germany), Fax: (+49)?228‐739616;2. Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia (Spain) |
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Abstract: | The reaction of Li/Cl P‐CPh3 phosphinidenoid tungsten(0) complex 2 with dimethylcyanamide afforded tricyclic phosphirane complex 4 , an unprecedented rearrangement of which led to the novel N,P,C cage complex 6 . On the basis of DFT calculations, formation and intramolecular 3+2] cycloaddition of the transient nitrilium phosphane ylide complex 3 to a phenyl ring of the triphenylmethyl substituent to give 4 is proposed. Furthermore, theoretical evidence for terminal N‐amidinophosphinidene complex 7 , formed by 2+1] cycloelimination from 4 , is provided, and the role of the electronic structure and non‐covalent interactions of intermediate 7 discussed. |
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Keywords: | cage compounds noncovalent interactions P ligands rearrangement tungsten |
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