Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer

Loose, Florian; Wang, Dian; Tian, Lei; Scholes, Gregory D.; Knowles, Robert R.; Chirik, Paul J.

doi:10.1039/C9CC01046G

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

Journal Article · Wed Apr 17 00:00:00 EDT 2019 · ChemComm

DOI:https://doi.org/10.1039/C9CC01046G· OSTI ID:1510786

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Princeton Univ., Princeton, NJ (United States)

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.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006498

OSTI ID:: 1510786

Alternate ID(s):: OSTI ID: 1509498

Journal Information:: ChemComm, Vol. 55, Issue 39; ISSN 1359-7345

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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