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

作者：Bhattacharya Papri; Heiden Zachariah M; Wiedner Eric S; Raugei Simone; Piro Nicholas A; Kassel W Scott; Bullock R Morris; Mock Michael T^*

来源：Journal of the American Chemical Society, 2017, 139(8): 2916-2919.

DOI：10.1021/jacs.7b00002

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](+).

• 出版日期2017-3-1