Terminal Uranium(V)-Nitride Hydrogenations Involving Direct Addition or Frustrated Lewis Pair Mechanisms

Lucile Chatelain, Elisa Louyriac, Iskander Douair, Erli Lu, Floriana Tuna, Ashley Wooles, Benedict Gardner, Laurent Maron, Stephen Liddle

Research output: Contribution to journalArticlepeer-review


Despite their importance as mechanistic models for heterogeneous Haber Bosch ammonia synthesis from dinitrogen and dihydrogen, homogeneous molecular terminal metal-nitrides are notoriously unreactive towards dihydrogen, and only a few electron-rich, low coordinate variants demonstrate any hydrogenolysis chemistry. Here, we report hydrogenolysis of a terminal uranium(V)-nitride under mild conditions even though it is electron-poor and not low-coordinate. Two divergent hydrogenolysis mechanisms are found; direct 1,2-dihydrogen addition across the uranium(V)- nitride then H-atom 1,1-migratory insertion to give a uranium(III)-amide, or with trimesitylborane a Frustrated Lewis Pair (FLP) route that produces a uranium(IV)-amide with sacrificial trimesitylborane radical anion. An isostructural uranium(VI)-nitride is inert to hydrogenolysis, suggesting the 5f1 electron of the uranium(V)-nitride is not purely non-bonding. Further FLP reactivity between the uranium(IV)-amide, dihydrogen, and triphenylborane is suggested by the formation of ammonia-triphenylborane. A reactivity cycle for ammonia synthesis is demonstrated, and this work establishes a unique marriage of actinide and FLP chemistries.
Original languageEnglish
Article number337
Pages (from-to)1-12
Number of pages12
JournalNature Communications
Issue number1
Publication statusPublished - 17 Jan 2020


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