Terminal uranium(V)-nitride hydrogenations involving direct addition or Frustrated Lewis Pair mechanisms

Lucile Chatelain, Elisa Louyriac, Iskander Douair, Erli Lu, Floriana Tuna, Ashley J. Wooles, Benedict M. Gardner, Laurent Maron () and Stephen T. Liddle ()
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Lucile Chatelain: The University of Manchester
Elisa Louyriac: LPCNO, CNRS & INSA, Université Paul Sabatier
Iskander Douair: LPCNO, CNRS & INSA, Université Paul Sabatier
Erli Lu: The University of Manchester
Floriana Tuna: The University of Manchester
Ashley J. Wooles: The University of Manchester
Benedict M. Gardner: The University of Manchester
Laurent Maron: LPCNO, CNRS & INSA, Université Paul Sabatier
Stephen T. Liddle: The University of Manchester

Nature Communications, 2020, vol. 11, issue 1, 1-12

Abstract: Abstract 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.

Date: 2020
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DOI: 10.1038/s41467-019-14221-y

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