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      Dinitrogen as a Universal Electron Acceptor in Solid-State Chemistry: An Example of Uncommon Metallic Compounds Na3(N2)4 and NaN2.

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          Abstract

          With the exception of lithium, alkali metals do not react with elemental nitrogen either at ambient conditions or at elevated temperatures, requiring the search for alternative synthetic routes to their nitrogen-containing compounds. Here using a controlled decomposition of sodium azide (NaN3) at high pressure conditions, we synthesize two novel compounds, Na3(N2)4 and NaN2, both containing dinitrogen anions. NaN2 synthesized at 4 GPa might be the common intermediate in high-pressure solid-state metathesis reactions, where NaN3 is used as a source of nitrogen, while Na3(N2)4 opens a new class of compounds, where [N2] units accommodate a noninteger formal charge of 0.75-. This finding can dramatically extend the expected compositions in other group 1 and 2 metal-nitrogen systems. Electronic structure calculations show the metallic character for both compounds.

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          Author and article information

          Journal
          Inorg Chem
          Inorganic chemistry
          American Chemical Society (ACS)
          1520-510X
          0020-1669
          Oct 19 2020
          : 59
          : 20
          Affiliations
          [1 ] Department of Mathematics, Howard University, Washington, DC 20059, United States.
          [2 ] The Earth and Planets Laboratory, Carnegie Institution for Science, Washington, DC 20015, United States.
          [3 ] U.S. Army Research Laboratory, RDRL-WML-B, Aberdeen Proving Ground, Maryland 21005, United States.
          [4 ] HPCAT, X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States.
          [5 ] Photon Science, Deutsches Elektronen-Synchrotron, Hamburg 22607, Germany.
          [6 ] Center for Advanced Radiation Sources, University of Chicago, Lemont, Illinois 60437, United States.
          Article
          10.1021/acs.inorgchem.0c01863
          33000943
          a5b0b926-ec17-4782-bd6e-f358d23e64f2
          History

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