Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand

Grant W. Margulieux, Máté J. Bezdek, Zoë R. Turner, Paul J. Chirik

Research output: Contribution to journalArticle

36 Scopus citations

Abstract

Treatment of the bis(imino)pyridine molybdenum η6-benzene complex (iPrPDI)Mo(η6-C6H6) (iPrPDI, 2,6-(2,6-iPr2C6H3NCMe)2C5H3N) with NH3 resulted in coordination induced haptotropic rearrangement of the arene to form (iPrPDI)Mo(NH3)22-C6H6). Analogous η2-ethylene and η2-cyclohexene complexes were also synthesized, and the latter was crystallographically characterized. All three compounds undergo loss of the η2-coordinated ligand followed by N-H bond activation, bis(imino)pyridine modification, and H2 loss. A dual ammonia activation approach has been discovered whereby reversible M-L cooperativity and coordination induced bond weakening likely contribute to dihydrogen formation. Significantly, the weakened N-H bonds in (iPrPDI)Mo(NH3)22-C2H4) enabled hydrogen atom abstraction and synthesis of a terminal nitride from coordinated ammonia, a key step in NH3 oxidation.

Original languageEnglish (US)
Pages (from-to)6110-6113
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number17
DOIs
StatePublished - May 3 2017

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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