Ammonia Synthesis by Hydrogenolysis of Titanium-Nitrogen Bonds Using Proton Coupled Electron Transfer

Iraklis Pappas, Paul J. Chirik

Research output: Contribution to journalArticle

41 Scopus citations

Abstract

The catalytic hydrogenolysis of the titanium-amide bond in (η5-C5Me4SiMe3)2Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (η5-C5Me5)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes and reveal a stark dependence on metal identity and oxidation state. In all cases, the N-H BDFEs of coordinated NH3 decreases by >40 kcal/mol from the value in the free gas phase molecule.

Original languageEnglish (US)
Pages (from-to)3498-3501
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number10
DOIs
StatePublished - Mar 18 2015

All Science Journal Classification (ASJC) codes

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

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