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

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

doi:10.1021/jacs.7b00002

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

J Am Chem Soc. 2017 Mar 1;139(8):2916-2919. doi: 10.1021/jacs.7b00002. Epub 2017 Feb 15.

Authors

Papri Bhattacharya¹, Zachariah M Heiden², Eric S Wiedner¹, Simone Raugei¹, Nicholas A Piro³, W Scott Kassel³, R Morris Bullock¹, Michael T Mock¹

Affiliations

¹ Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
² Department of Chemistry, Washington State University , Pullman, Washington 99164, United States.
³ Department of Chemistry, Villanova University , Villanova, Pennsylvania 19085, United States.

PMID: 28166403
DOI: 10.1021/jacs.7b00002

Abstract

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]⁺.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.