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Updated: Sep 13, 2025

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Stepwise azido transfer to cerous tris(tert-butoxy)siloxide via trans-silylation with Me3SiN3
Jochen Friedrich1, Jonas Riedmaier1, Cäcilia Maichle-Mössmer1
1Institut für Anorganische Chemie; Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany. reiner.anwander@uni-tuebingen.de.
Abstract:
Trimethylsilylhalogenides and -pseudohalogenides are frequently used reactants for (pseudo)halogen transfer, including derivatizations of cerium compounds. The present study describes the facile ligand exchange of cerium(III) complex [Ce{OSi(OtBu)3}3]2 with Me3SiN3 generating the mixed azido/siloxy CeIII complexes Ce2[OSi(OtBu)3]5(N3) and [Ce{OSi(OtBu)3}2(N3)]4. Although cerium siloxide complexes are a topical research field, thermal or photolytic ligand degradation as described in CeIV alkoxide chemistry has not been described. The activation of the azide complexes by irradiation with UV-visible light is easily achieved for such mixed azido/siloxy cerous complexes, as revealed by the identification of the homoleptic ceric complex Ce[OSi(OtBu)3]4.
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