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The Triple‐Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage
Author(s) -
Lackner Aaron D.,
Fürstner Alois
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201506546
Subject(s) - metathesis , chemistry , triple bond , molybdenum , nitrile , salt metathesis reaction , cleavage (geology) , salt (chemistry) , bond cleavage , ligand (biochemistry) , polymer chemistry , tungsten , metal , combinatorial chemistry , medicinal chemistry , organic chemistry , double bond , catalysis , materials science , biochemistry , receptor , fracture (geology) , composite material , polymerization , polymer
The {N 2 } 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 {N 2 }→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.