Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH_3 Complex

摘要

We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH_3]~+ 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-l-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-NH_3]~+ and formation of [Mo=NR]~+.