Journal of the American Chemical Society, Vol.139, No.8, 2916-2919, 2017
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 equivalent to 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](+).