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Updated: Oct 4, 2025

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Synthesis of azadiphosphiridine complexes. Theoretical studies on ring formation, the P-to-P' metal shift and the
Alexander Schmer1, Antonio García Alcaraz2, Andreas Wolfgang Kyri1
1Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhards-Domagk-Str. 1, 53121 Bonn, Germany. r.streubel@uni-bonn.de.
Abstract:
A set of azadiphosphiridine complexes 3a and 4b,c were synthesized in high selectivity using N-H and P-H deprotonation as key steps and RPCl2 as substrates (R = NiPr2 (a), -Bu (b), Ph (c)). While complex 3a (P-NiPr2) retained the P-W linkage of the starting material W(CO)5{Ph3CP(H)NH}, complexes 4b (P-Bu) and 4c (P-Ph) revealed that a P-to-P' haptotropic shift of the W(CO)5 group has occurred. Remarkably, complex 3a, bearing an unligated P-NiPr2 unit, displays a planar ring N geometry while 4b,c showed a pyramidal geometry of the ring nitrogen atom. Theoretical studies on the ring formation including the P-to-P' haptotropic metal shift and the factors influencing the ring nitrogen geometry are reported.
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