Catalytic and stoichiometric stepwise conversion of side-on bound dinitrogen to ammonia mediated by a uranium complex
Year: 2025
Type: article
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.
Source: Nature Chemistry
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $12,690
Funders: National Science Foundation, Alexander von Humboldt-Stiftung, UK Research and Innovation, Research Councils UK, University of Manchester, École Polytechnique Fédérale de Lausanne, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, Engineering and Physical Sciences Research Council
Awards: G2284755829, sigma-Aromatic Actinide-Actinide Bonding: A New Frontier in f-Block Chemistry, EPSRC Centre for Doctoral Training in Integrated Catalysis, G3201850698, G4187837619, G4546342991, G4838032633, National Nuclear User Facility at the Centre for Radiochemistry Research (CRR), Uranium-Ligand Multiple Bonds: From Molecules to Materials, G6524049574, G6795884900, DESIGN OF MULTIMETALLIC COMPLEXES OF F-ELEMENTS IN UNUSUAL OXIDATION STATES: ACTIVATION AND FUNCTIONALIZATION OF DINITROGEN AND MAGNETIC PROPERTIES
OpenAlex ID: W4412470306