Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction

Authors

Papri Bhattacharya, Zachariah M Heiden, Geoffrey M Chambers, Samantha I Johnson, R Morris Bullock, Michael T Mock

Publication

Angewandte Chemie

Abstract

Catalysts for the oxidation of NH3 are critical for the utilization of NH3 as a large?scale energy carrier. Molecular catalysts capable of oxidizing NH3 to N2 are rare. This report describes the use of [Cp*Ru(PtBu2NPh2)(15NH3)][BArF4], (PtBu2NPh2=1,5?di(phenylaza)?3,7?di(tert?butylphospha)cyclooctane; ArF=3,5?(CF3)2C6H3), to catalytically oxidize NH3 to dinitrogen under ambient conditions. The cleavage of six N?H bonds and the formation of an N?N bond was achieved by coupling H+ and e? transfers as net hydrogen atom abstraction (HAA) steps using the 2,4,6?tri?tert?butylphenoxyl radical (tBu3ArO.) as the H atom acceptor. Employing an excess of tBu3ArO. under 1?atm of NH3 gas at 23?°C resulted in up to ten turnovers. Nitrogen isotopic (15N) labeling studies provide initial mechanistic information suggesting a monometallic pathway during the N???N bond?forming step in the catalytic cycle.

Links

 

How is this information collected?

This collection of Montana State authored publications is collected by the Library to highlight the achievements of Montana State researchers and more fully understand the research output of the University. They use a number of resources to pull together as complete a list as possible and understand that there may be publications that are missed. If you note the omission of a current publication or want to know more about the collection and display of this information email Leila Sterman.