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Nitride

Not to be confused with nitrite, nitrate, or nitrogen dioxide.

In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitrides have a found applications,[1] such as wear-resistant coatings (e.g., titanium nitride, TiN), hard ceramic materials (e.g., silicon nitride, Si3N4), and semiconductors (e.g., gallium nitride, GaN). The development of GaN-based light emitting diodes was recognized by the 2014 Nobel Prize in Physics.[2] Metal nitrido complexes are also common.

Synthesis of inorganic metal nitrides is challenging because nitrogen gas (N2) is not very reactive at low temperatures, but it becomes more reactive at higher temperatures. Therefore, a balance must be achieved between the low reactivity of nitrogen gas at low temperatures and the entropy driven formation of N2 at high temperatures.[3] However, synthetic methods for nitrides are growing more sophisticated and the materials are of increasing technological relevance.[4]

Uses of nitrides

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Like carbides, nitrides are often refractory materials owing to their high lattice energy, which reflects the strong bonding of "N3−" to metal cation(s). Thus, cubic boron nitride, titanium nitride, and silicon nitride are used as cutting materials and hard coatings. Hexagonal boron nitride, which adopts a layered structure, is a useful high-temperature lubricant akin to molybdenum disulfide. Nitride compounds often have large band gaps, thus nitrides are usually insulators or wide-bandgap semiconductors; examples include boron nitride and silicon nitride. The wide-band gap material gallium nitride is prized for emitting blue light in LEDs.[5][6] Like some oxides, nitrides can absorb hydrogen and have been discussed in the context of hydrogen storage, e.g. lithium nitride.

Examples

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Classification of such a varied group of compounds is somewhat arbitrary. Compounds where nitrogen is not assigned −3 oxidation state are not included, such as nitrogen trichloride where the oxidation state is +3; nor are ammonia and its many organic derivatives.

Nitrides of the s-block elements

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Only one alkali metal nitride is stable, the purple-reddish lithium nitride (Li3N), which forms when lithium burns in an atmosphere of N2.[7] Sodium nitride and potassium nitride has been generated, but remains a laboratory curiosity. The nitrides of the alkaline earth metals that have the formula M3N2 are however numerous. Examples include beryllium nitride (Be3N2), magnesium nitride (Mg3N2), calcium nitride (Ca3N2), and strontium nitride (Sr3N2). The nitrides of electropositive metals (including Li, Zn, and the alkaline earth metals) readily hydrolyze upon contact with water, including the moisture in the air:

Mg3N2 + 6 H2O → 3 Mg(OH)2 + 2 NH3

Nitrides of the p-block elements

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Boron nitride exists as several forms (polymorphs). Nitrides of silicon and phosphorus are also known, but only the former is commercially important. The nitrides of aluminium, gallium, and indium adopt the hexagonal wurtzite structure in which each atom occupies tetrahedral sites. For example, in aluminium nitride, each aluminium atom has four neighboring nitrogen atoms at the corners of a tetrahedron and similarly each nitrogen atom has four neighboring aluminium atoms at the corners of a tetrahedron. This structure is like hexagonal diamond (lonsdaleite) where every carbon atom occupies a tetrahedral site (however wurtzite differs from sphalerite and diamond in the relative orientation of tetrahedra). Thallium(I) nitride (Tl3N) is known, but thallium(III) nitride (TlN) is not.

Transition metal nitrides

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See also: Zirconium nitride, Tungsten nitride, Vanadium nitride, Tantalum nitride, Niobium nitride, and Mercury nitride

Most metal-rich transition metal nitrides adopt a relatively ordered face-centered cubic or hexagonal close-packed crystal structure, with octahedral coordination.[8] Sometimes these materials are called "interstitial nitrides". They are essential for industrial metallurgy, because they are typically much harder and less ductile than their parent metal, and resist air-oxidation.[9] For the group 3 metals, ScN and YN are both known. Group 4, 5, and 6 transition metals (the titanium, vanadium and chromium groups) all form[10] chemically stable, refractory nitrides with high melting point. Thin films of titanium nitride, zirconium nitride, and tantalum nitride protect many industrial surfaces.

Nitrides of the group 7 and 8 transition metals tend to be nitrogen-poor, and decompose readily at elevated temperatures. For example, iron nitride, Fe2N decomposes at 200 °C. Platinum nitride and osmium nitride may contain N2 units, and as such should not be called nitrides.[11][12]

Nitrides of heavier members from group 11 and 12 are less stable than copper nitride (Cu3N) and zinc nitride (Zn3N2): dry silver nitride (Ag3N) is a contact explosive which may detonate from the slightest touch, even a falling water droplet.[13]

Nitrides of the lanthanides and actinides

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Nitride containing species of the lanthanides and actinides are of scientific interest as they can provide a useful handle for determining covalency of bonding. Nuclear magnetic resonance (NMR) spectroscopy along with quantum chemical analysis has often been used to determine the degree to which metal nitride bonds are ionic or covalent in character. One example, a uranium nitride, has the highest known nitrogen-15 chemical shift.[14]

Molecular nitrides

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S4N4 is a prototypical binary molecular nitride.
Main article: Transition metal nitrido complex

Many metals form molecular nitrido complexes, as discussed in the specialized article. The main group elements also form some molecular nitrides. Cyanogen ((CN)2) and tetrasulfur tetranitride (S4N4) are rare examples of a molecular binary (containing one element aside from nitrogen) nitrides. They dissolve in nonpolar solvents. Both undergo polymerization. S4N4 is also unstable with respect to the elements, but less so that the isostructural Se4N4. Heating S4N4 gives a polymer, and a variety of molecular sulfur nitride anions and cations are also known.

Related to but distinct from nitride is pernitride diatomic anion (N2−2) and the azide triatomic anion (N3-).

References

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  1. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  2. ^ "The Nobel Prize in Physics 2014". The Nobel Prize. Nobel Prize Outreach. Retrieved 13 January 2021.
  3. ^ Sun, Wenhao; Bartel, Christopher J.; Arca, Elisabetta; Bauers, Sage R.; Matthews, Bethany; Orvañanos, Bernardo; Chen, Bor-Rong; Toney, Michael F.; Schelhas, Laura T.; Tumas, William; Tate, Janet; Zakutayev, Andriy; Lany, Stephan; Holder, Aaron M.; Ceder, Gerbrand (2019). "A map of the inorganic ternary metal nitrides". Nature Materials. 18 (7): 732–739. arXiv:1809.09202. doi:10.1038/s41563-019-0396-2. ISSN 1476-4660. PMID 31209391. S2CID 119461695.
  4. ^ Greenaway, Ann L.; Melamed, Celeste L.; Tellekamp, M. Brooks; Woods-Robinson, Rachel; Toberer, Eric S.; Neilson, James R.; Tamboli, Adele C. (2021-07-26). "Ternary Nitride Materials: Fundamentals and Emerging Device Applications". Annual Review of Materials Research. 51 (1): 591–618. arXiv:2010.08058. doi:10.1146/annurev-matsci-080819-012444. ISSN 1531-7331. S2CID 223953608.
  5. ^ Oyama, S. T., ed. (1996). The Chemistry of Transition Metal Carbides and Nitrides. Blackie Academic. ISBN 0-7514-0365-2.
  6. ^ Pierson, H. O. (1996). Handbook of refractory carbides and nitrides. William Andrew. ISBN 0-8155-1392-5.
  7. ^ Gregory, Duncan H. (2001). "Nitride chemistry of the s-block elements". Coord. Chem. Rev. 215: 301–345. doi:10.1016/S0010-8545(01)00320-4.
  8. ^ Toth, Louis (2014-04-11). Transition Metal Carbides and Nitrides. Elsevier. ISBN 978-0-323-15722-3.
  9. ^ Leineweber, Andreas; Niewa, Rainer; Jacobs, Herbert; Kockelmann, Winfried (2000). "The manganese nitrides η‐Mn3N2 and θ‐Mn6N5 + x: nuclear and magnetic structures". Journal of Materials Chemistry. 10 (12): 2827–2834. doi:10.1039/b006969h.
  10. ^ Mei, A. B.; Howe, B. M.; Zhang, C.; Sardela, M.; Eckstein, J. N.; Hultman, L.; Rockett, A.; Petrov, I.; Greene, J. E. (2013-10-18). "Physical properties of epitaxial ZrN/MgO(001) layers grown by reactive magnetron sputtering". Journal of Vacuum Science & Technology A. 31 (6): 061516. Bibcode:2013JVSTA..31f1516M. doi:10.1116/1.4825349. ISSN 0734-2101.
  11. ^ Siller, L.; Peltekis, N.; Krishnamurthy, S.; Chao, Y.; Bull, S. J.; Hunt, M. R. C. (2005). "Gold film with gold nitride—A conductor but harder than gold" (PDF). Appl. Phys. Lett. 86 (22): 221912. Bibcode:2005ApPhL..86v1912S. doi:10.1063/1.1941471.
  12. ^ Montoya, J. A.; Hernández, A. D.; Sanloup, C.; Gregoryanz, E.; Scandolo, S (2007). "OsN2: Crystal structure and electronic properties". Appl. Phys. Lett. 90 (1): 011909. Bibcode:2007ApPhL..90a1909M. doi:10.1063/1.2430631.
  13. ^ Shanley, Edward S.; Ennis, John L. (1991). "The Chemistry and Free Energy Formation of Silver Nitride". Ind. Eng. Chem. Res. 30 (11): 2503. doi:10.1021/ie00059a023.
  14. ^ Du, Jingzhen; Seed, John A.; Berryman, Victoria E. J.; Kaltsoyannis, Nikolas; Adams, Ralph W.; Lee, Daniel; Liddle, Stephen T. (2021). "Exceptional uranium(VI)-nitride triple bond covalency from 15N nuclear magnetic resonance spectroscopy and quantum chemical analysis". Nat. Commun. 12 (1): 5649. Bibcode:2021NatCo..12.5649D. doi:10.1038/s41467-021-25863-2. PMC 8463702. PMID 34561448.

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