Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH₃ Complex

We report ammonia oxidation by homolytic cleavage of all three H atoms from a [MoNH3]+ complex using the 2,4,6-tri-tert-butylphenoxyl radical to yield a Mo-alkylimido ([MoNR]+) complex (R = 2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one). Chemical reduction of [MoNR]+ generates a terminal MoN nitride complex upon NC bond cleavage, and a [MoNH]+ complex is formed by protonation of the nitride. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from [MoNH3]+ and formation of [MoNR]+.