Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

Bjorn Askevold, Jorge Torres Nieto, Samat Tussupbayev, Martin Diefenbach, Eberhardt Herdtweck, Max C. Holthausen, Sven Schneider

Research output: Contribution to journalArticlepeer-review

150 Scopus citations


Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with μ-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H2 at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting.

Original languageEnglish (US)
Pages (from-to)532-537
Number of pages6
JournalNature Chemistry
Issue number7
StatePublished - May 1 2011

Fingerprint Dive into the research topics of 'Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand'. Together they form a unique fingerprint.

Cite this