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Schneider SB, Seibald M, Deringer VL, et al. High-pressure synthesis and characterization of Li2Ca3[N2]3--an uncommon metallic diazenide with [N2]2- ions. J Am Chem Soc. 2013;135(44):16668-79doi: 10.1021/ja408816t.
Schneider, S. B., Seibald, M., Deringer, V. L., Stoffel, R. P., Frankovsky, R., Friederichs, G. M., Laqua, H., Duppel, V., Jeschke, G., Dronskowski, R., & Schnick, W. (2013). High-pressure synthesis and characterization of Li2Ca3[N2]3--an uncommon metallic diazenide with [N2]2- ions. Journal of the American Chemical Society, 135(44), 16668-79. https://doi.org/10.1021/ja408816t
Schneider, Sebastian B, et al. "High-pressure synthesis and characterization of Li2Ca3[N2]3--an uncommon metallic diazenide with [N2]2- ions." Journal of the American Chemical Society vol. 135,44 (2013): 16668-79. doi: https://doi.org/10.1021/ja408816t
Schneider SB, Seibald M, Deringer VL, Stoffel RP, Frankovsky R, Friederichs GM, Laqua H, Duppel V, Jeschke G, Dronskowski R, Schnick W. High-pressure synthesis and characterization of Li2Ca3[N2]3--an uncommon metallic diazenide with [N2]2- ions. J Am Chem Soc. 2013 Nov 06;135(44):16668-79. doi: 10.1021/ja408816t. PMID: 24090235.
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J Am Chem Soc. 2013 Nov 06;135(44):16668-79. doi: 10.1021/ja408816t.

High-pressure synthesis and characterization of Li2Ca3[N2]3--an uncommon metallic diazenide with [N2]2- ions.

Journal of the American Chemical Society

Sebastian B Schneider, Markus Seibald, Volker L Deringer, Ralf P Stoffel, Rainer Frankovsky, Gina M Friederichs, Henryk Laqua, Viola Duppel, Gunnar Jeschke, Richard Dronskowski, Wolfgang Schnick

PMID: 24090235 DOI: 10.1021/ja408816t

Abstract

Dinitrogen (N2) ligation is a common and well-characterized structural motif in bioinorganic synthesis. In solid-state chemistry, on the other hand, homonuclear dinitrogen entities as structural building units proved existence only very recently. High-pressure/high-temperature (HP/HT) syntheses have afforded a number of binary diazenides and pernitrides with [N2](2–) and [N2](4–) ions, respectively. Here, we report on the HP/HT synthesis of the first ternary diazenide. Li2Ca3[N2]3 (space group Pmma, no. 51, a = 4.7747(1), b = 13.9792(4), c = 8.0718(4) Å, Z = 4, wRp = 0.08109) was synthesized by controlled thermal decomposition of a stoichiometric mixture of lithium azide and calcium azide in a multianvil device under a pressure of 9 GPa at 1023 K. Powder X-ray diffraction analysis reveals strongly elongated N–N bond lengths of dNN = 1.34(2)–1.35(3) Å exceeding those of previously known, binary diazenides. In fact, the refined N–N distances in Li2Ca3[N2]3 would rather suggest the presence of [N2](3·–) radical ions. Also, characteristic features of the N–N stretching vibration occur at lower wavenumbers (1260–1020 cm(–1)) than in the binary phases, and these assignments are supported by first-principles phonon calculations. Ultimately, the true character of the N2 entity in Li2Ca3[N2]3 is probed by a variety of complementary techniques, including electron diffraction, electron spin resonance spectroscopy (ESR), magnetic and electric conductivity measurements, as well as density-functional theory calculations (DFT). Unequivocally, the title compound is shown to be metallic containing diazenide [N2](2–) units according to the formula (Li(+))2(Ca(2+))3([N2](2–))3·(e(–))2.

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