The azaphosphiridine to terminal phosphinidene complex rearrangement--looking for non-covalent interactions of a highly reactive species
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Updated: May 8, 2026

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
José Manuel Villalba Franco1, Arturo Espinosa Ferao, Gregor Schnakenburg
1Institut für Anorganische Chemie der Reinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str.1, 53121 Bonn, Germany. r.streubel@uni-bonn.de.
Abstract:
Azaphosphiridine complexes 4a,a', intermediates in the reaction of P-C5Me5 substituted Li–Cl phosphinidenoid complex 2 and C-furyl carbaldimine 3, rearranged selectively to give the novel N,P,C-cage complex 5a. Transient terminal phosphinidene complex 7a was trapped with phenyl acetylene (8) forming the new N,P,C-cage complex 9. DFT calculations provide evidence for a thermally allowed aza-phospha-Cope rearrangement that led to the P-amino substituted phosphinidene complex 7a, which is stabilized by non-covalent interactions in addition to typical through-bond electronic effects.
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Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...

