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

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

Research output: Contribution to journalArticle

5 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)5595-5598
Number of pages4
JournalChemical Communications
Volume55
Issue number39
DOIs
StatePublished - Jan 1 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Chemistry(all)
  • Surfaces, Coatings and Films
  • Metals and Alloys
  • Materials Chemistry

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