Reaction of (Bisimido)niobium(V) Complexes with Organic Azides: [3 + 2] Cycloaddition and Reversible Cleavage of β‑Diketiminato Ligands Involving Nitrene Transfer

We describe the unusual reactivity of a highly labile diethyl ether adduct of an asymmetric niobium(V) bis(imide) 2.OEt 2 containing the mono­azabuta­diene (MAD) ligand. This species undergoes clean nitrene transfer on treatment with tert-butyl- or di-iso­propyl­phenyl azide resulting in the unprece...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-02, Vol.136 (8), p.2994-2997
Main Authors: Obenhuber, Andreas H, Gianetti, Thomas L, Berrebi, Xavier, Bergman, Robert G, Arnold, John
Format: Article
Language:English
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Summary:We describe the unusual reactivity of a highly labile diethyl ether adduct of an asymmetric niobium(V) bis(imide) 2.OEt 2 containing the mono­azabuta­diene (MAD) ligand. This species undergoes clean nitrene transfer on treatment with tert-butyl- or di-iso­propyl­phenyl azide resulting in the unprecedented reformation of nacnac ligands bound to the metal center. Corresponding reactions with tri­methyl­silyl- or tert-butyl azide allowed the isolation of two rare intermediates prior to N2 loss; mechanistic studies support the involvement of two different niobium species.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja413194z