N-H Bond Formation in a Manganese(V) Nitride Yields Ammonia by Light-Driven Proton-Coupled Electron Transfer

Dian Wang; Florian Loose; Paul J Chirik; Robert R Knowles

doi:10.1021/jacs.8b12957

N-H Bond Formation in a Manganese(V) Nitride Yields Ammonia by Light-Driven Proton-Coupled Electron Transfer

J Am Chem Soc. 2019 Mar 27;141(12):4795-4799. doi: 10.1021/jacs.8b12957. Epub 2019 Mar 5.

Authors

Dian Wang¹, Florian Loose¹, Paul J Chirik¹, Robert R Knowles¹

Affiliation

¹ Department of Chemistry , Princeton University , Princeton , New Jersey 08544 , United States.

PMID: 30803234
DOI: 10.1021/jacs.8b12957

Abstract

A method for the reduction of a manganese nitride to ammonia is reported, where light-driven proton-coupled electron transfer enables the formation of weak N-H bonds. Photoreduction of (sal^tBu)Mn^VN to ammonia and a Mn(II) complex has been accomplished using 9,10-dihydroacridine and a combination of an appropriately matched photoredox catalyst and weak Brønsted acid. Acid-reductant pairs with effective bond dissociation free energies between 35 and 46 kcal/mol exhibited high efficiencies. This light-driven method may provide a blueprint for new approaches to catalytic homogeneous ammonia synthesis under ambient conditions.

Publication types

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