A Novel N, P, C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non‐covalent Interactions. Issue 23 (15th April 2014)

• Record Type: Journal Article
• Authors: Nesterov, Vitaly; Espinosa, Arturo; Schnakenburg, Gregor; Streubel, Rainer
• Is Part Of: Chemistry. Volume 20:Issue 23(2014)
• Page Start: 7010
• Page End: 7016
• Publication Date: 2014-04-15
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201305061
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reaction of Li/Cl <italic>P</italic>‐CPh₃ phosphinidenoid tungsten(0) complex <bold>2</bold> with dimethylcyanamide afforded tricyclic phosphirane complex <bold>4</bold>, an unprecedented rearrangement of which led to the novel N, P, C cage complex <bold>6</bold>. On the basis of DFT calculations, formation and intramolecular [3+2] cycloaddition of the transient nitrilium phosphane ylide complex <bold>3</bold> to a phenyl ring of the triphenylmethyl substituent to give <bold>4</bold> is proposed. Furthermore, theoretical evidence for terminal <italic>N</italic>‐amidinophosphinidene complex <bold>7</bold>, formed by [2+1] cycloelimination from <bold>4</bold>, is provided, and the role of the electronic structure and non‐covalent interactions of intermediate <bold>7</bold> discussed.</p> </abstract>