Dinitrogen as a Universal Electron Acceptor in Solid-State Chemistry: An Example of Uncommon Metallic Compounds Na3(N2)4 and NaN2
Abstract
With the exception of Li, alkali metals do not react with elemental nitrogen neither at ambient conditions nor 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 non-integer formal charge of -0.75. This finding can dramatically extend the expected compositions in other group 1-2 metal-nitrogen systems. Electronic structure calculations show the metallic character for both compounds.
- Authors:
-
[1];
[2];
[3];
- Howard Univ., Washington, DC (United States); Carnegie Inst. of Science, Washington, DC (United States)
- Army Research Lab., Adelphi, MD (United States)
- Carnegie Inst. of Science, Argonne, IL (United States). High Pressure Collaborative Access Team (HPCAT); Argonne National Lab. (ANL), Argonne, IL (United States)
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Photon Science
- Univ. of Chicago, IL (United States)
- Howard Univ., Washington, DC (United States)
- Carnegie Inst. of Science, Washington, DC (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA), Office of Experimental Sciences; National Science Foundation (NSF)
- OSTI Identifier:
- 1686110
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 20; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; High-pressure chemistry; azides; diazenides; nitrides; nitrogen; nitrogen fixation; pernitride; sodium azide; anions; organic reactions
Citation Formats
Bykov, Maxim, Tasca, Kelin R., Batyrev, Iskander G., Smith, Dean, Glazyrin, Konstantin, Chariton, Stella, Mahmood, Mohammad, and Goncharov, Alexander F. Dinitrogen as a Universal Electron Acceptor in Solid-State Chemistry: An Example of Uncommon Metallic Compounds Na3(N2)4 and NaN2. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.0c01863.
Bykov, Maxim, Tasca, Kelin R., Batyrev, Iskander G., Smith, Dean, Glazyrin, Konstantin, Chariton, Stella, Mahmood, Mohammad, & Goncharov, Alexander F. Dinitrogen as a Universal Electron Acceptor in Solid-State Chemistry: An Example of Uncommon Metallic Compounds Na3(N2)4 and NaN2. United States. https://doi.org/10.1021/acs.inorgchem.0c01863
Bykov, Maxim, Tasca, Kelin R., Batyrev, Iskander G., Smith, Dean, Glazyrin, Konstantin, Chariton, Stella, Mahmood, Mohammad, and Goncharov, Alexander F. Thu .
"Dinitrogen as a Universal Electron Acceptor in Solid-State Chemistry: An Example of Uncommon Metallic Compounds Na3(N2)4 and NaN2". United States. https://doi.org/10.1021/acs.inorgchem.0c01863. https://www.osti.gov/servlets/purl/1686110.
@article{osti_1686110,
title = {Dinitrogen as a Universal Electron Acceptor in Solid-State Chemistry: An Example of Uncommon Metallic Compounds Na3(N2)4 and NaN2},
author = {Bykov, Maxim and Tasca, Kelin R. and Batyrev, Iskander G. and Smith, Dean and Glazyrin, Konstantin and Chariton, Stella and Mahmood, Mohammad and Goncharov, Alexander F.},
abstractNote = {With the exception of Li, alkali metals do not react with elemental nitrogen neither at ambient conditions nor 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 non-integer formal charge of -0.75. This finding can dramatically extend the expected compositions in other group 1-2 metal-nitrogen systems. Electronic structure calculations show the metallic character for both compounds.},
doi = {10.1021/acs.inorgchem.0c01863},
journal = {Inorganic Chemistry},
number = 20,
volume = 59,
place = {United States},
year = {Thu Oct 01 00:00:00 EDT 2020},
month = {Thu Oct 01 00:00:00 EDT 2020}
}
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