Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer
Abstract
Concepts for the thermodynamically challenging synthesis of weak N–H bonds by photoinduced proton coupled electron transfer are explored. Upon irradiation with blue light, ammonia synthesis was achieved from the manganese nitride (tBuSalen)MnN (tBuSalen = (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) in the presence of 9,10-dihydroacridine and a ruthenium photocatalyst in iPrOH solution. Although in one case the ruthenium complex bears a remote N–H bond that weakens to 41 kcal mol–1 upon irradiation, control experiments with the N-methylated analog demonstrate the ruthenium complex serves as a photoreductant rather than hydrogen-atom transfer catalyst in aprotic solvents. Luminescence quenching experiments support a ruthenium(II)/(III) cycle rather than a ruthenium(I)/(II) alternative. Identification of the manganese complex following ammonia synthesis was also accomplished.
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1510786
- Alternate Identifier(s):
- OSTI ID: 1509498
- Grant/Contract Number:
- SC0006498
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemComm
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 39; Journal ID: ISSN 1359-7345
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Loose, Florian, Wang, Dian, Tian, Lei, Scholes, Gregory D., Knowles, Robert R., and Chirik, Paul J. Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer. United States: N. p., 2019.
Web. doi:10.1039/C9CC01046G.
Loose, Florian, Wang, Dian, Tian, Lei, Scholes, Gregory D., Knowles, Robert R., & Chirik, Paul J. Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer. United States. https://doi.org/10.1039/C9CC01046G
Loose, Florian, Wang, Dian, Tian, Lei, Scholes, Gregory D., Knowles, Robert R., and Chirik, Paul J. Wed .
"Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer". United States. https://doi.org/10.1039/C9CC01046G. https://www.osti.gov/servlets/purl/1510786.
@article{osti_1510786,
title = {Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer},
author = {Loose, Florian and Wang, Dian and Tian, Lei and Scholes, Gregory D. and Knowles, Robert R. and Chirik, Paul J.},
abstractNote = {Concepts for the thermodynamically challenging synthesis of weak N–H bonds by photoinduced proton coupled electron transfer are explored. Upon irradiation with blue light, ammonia synthesis was achieved from the manganese nitride (tBuSalen)MnN (tBuSalen = (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) in the presence of 9,10-dihydroacridine and a ruthenium photocatalyst in iPrOH solution. Although in one case the ruthenium complex bears a remote N–H bond that weakens to 41 kcal mol–1 upon irradiation, control experiments with the N-methylated analog demonstrate the ruthenium complex serves as a photoreductant rather than hydrogen-atom transfer catalyst in aprotic solvents. Luminescence quenching experiments support a ruthenium(II)/(III) cycle rather than a ruthenium(I)/(II) alternative. Identification of the manganese complex following ammonia synthesis was also accomplished.},
doi = {10.1039/C9CC01046G},
journal = {ChemComm},
number = 39,
volume = 55,
place = {United States},
year = {Wed Apr 17 00:00:00 EDT 2019},
month = {Wed Apr 17 00:00:00 EDT 2019}
}
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