The Triple‐Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage |
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Authors: | Dr Aaron D Lackner Prof Alois Fürstner |
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Institution: | Max‐Planck‐Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany) |
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Abstract: | 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. |
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Keywords: | alkylidynes aryldiazonium salts metathesis molybdenum tungsten |
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