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

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 (saltBu)MnVN 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 35–46 kcal/mol exhibited high efficiencies. As a result, this light-driven method may provide a blueprint for new approaches to catalytic homogenous ammonia synthesis under ambient conditions.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Princeton Univ., Princeton, NJ (United States)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1506845
Grant/Contract Number:  
SC0006498
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 12; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Dian, Loose, Florian, Chirik, Paul J., and Knowles, Robert R. N–H Bond Formation in a Manganese(V) Nitride Yields Ammonia by Light-Driven Proton-Coupled Electron Transfer. United States: N. p., 2019. Web. doi:10.1021/jacs.8b12957.
Wang, Dian, Loose, Florian, Chirik, Paul J., & Knowles, Robert R. N–H Bond Formation in a Manganese(V) Nitride Yields Ammonia by Light-Driven Proton-Coupled Electron Transfer. United States. https://doi.org/10.1021/jacs.8b12957
Wang, Dian, Loose, Florian, Chirik, Paul J., and Knowles, Robert R. Mon . "N–H Bond Formation in a Manganese(V) Nitride Yields Ammonia by Light-Driven Proton-Coupled Electron Transfer". United States. https://doi.org/10.1021/jacs.8b12957. https://www.osti.gov/servlets/purl/1506845.
@article{osti_1506845,
title = {N–H Bond Formation in a Manganese(V) Nitride Yields Ammonia by Light-Driven Proton-Coupled Electron Transfer},
author = {Wang, Dian and Loose, Florian and Chirik, Paul J. and Knowles, Robert R.},
abstractNote = {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 (saltBu)MnVN 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 35–46 kcal/mol exhibited high efficiencies. As a result, this light-driven method may provide a blueprint for new approaches to catalytic homogenous ammonia synthesis under ambient conditions.},
doi = {10.1021/jacs.8b12957},
journal = {Journal of the American Chemical Society},
number = 12,
volume = 141,
place = {United States},
year = {2019},
month = {2}
}

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