Catalytic and stoichiometric stepwise conversion of side-on bound dinitrogen to ammonia mediated by a uranium complex

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Abstract
The well-defined catalytic conversion of dinitrogen (N2) to ammonia (NH3) by molecular complexes is of fundamental interest and important for providing an atomic-level understanding of reactivity that can be related to industrial and biological nitrogen-fixation processes. Molecular catalytic N2 to NH3 conversion currently involves the reduction and protonation of terminal or bridging end-on bound metal–N2 complexes. However, catalytic N2 to NH3 conversion by side-on bound metal–N2 molecular complexes is relevant to both the industrial and biological nitrogen-fixation processes. Here, using a uranium triamidoamine complex, we report catalytic N2 to NH3 conversion involving side-on bound N2 binding. Stoichiometric reactions reveal stepwise reduction of N2 from free N2 to bridging side-on bound forms and subsequently to bridging nitrides, uniquely accessing four different states of side-on bound N2 for the same molecular system. This reveals the roles of N2, N2 2−, N2 3−, N2 4− and N3− in the catalytic conversion of N2 to NH3 when involving side-on bridging N2.
Funding Information
  • École Polytechnique Fédérale de Lausanne
  • Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung (236428, 212723, 212723)
  • RCUK | Engineering and Physical Sciences Research Council (EP/S023755/1, EP/M027015/1, EP/T011289/1, EP/W029057/1, EP/M027015/1, EP/T011289/1, EP/W029057/1, EP/M027015/1, EP/T011289/1, EP/W029057/1, EP/M027015/1, EP/T011289/1, EP/W029057/1)

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