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The Triple-Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage

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Lackner,  Aaron D.
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Zitation

Lackner, A. D., & Fürstner, A. (2015). The Triple-Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage. Angewandte Chemie International Edition, 54(43), 12814-12818. doi:10.1002/anie.201506546.


Zitierlink: https://hdl.handle.net/11858/00-001M-0000-0028-EFE1-3
Zusammenfassung
The {N2} unit of aryldiazonium salts undergoes unusually facile triple-bond metathesis on treatment with molybdenum or tungsten alkylidyne ate complexes endowed with triphenylsilanolate ligands. The reaction transforms the alkylidyne unit into a nitrile and the aryldiazonium entity into an imido ligand on the metal center, as unambiguously confirmed by X-ray structure analysis of two representative examples. A tungsten nitride ate complex is shown to react analogously. Since the bonding situation of an aryldiazonium salt is similar to that of metal complexes with end-on-bound dinitrogen, in which {N2}→M σ donation is dominant and electron back donation minimal, the metathesis described herein is thought to be a conceptually novel strategy toward dinitrogen cleavage devoid of any redox steps and, therefore, orthogonal to the established methods.