Electride

An electride is an ionic compound in which an electron is the anion.[1] Solutions of alkali metals in ammonia are electride salts.[2] In the case of sodium, these blue solutions consist of [Na(NH3)6]+ and solvated electrons:

Na + 6 NH3 → [Na(NH3)6]+,e−
Cavities and channels in an electride

The cation [Na(NH3)6]+ is an octahedral coordination complex.

Solid salts

Addition of a complexant like crown ether or 2,2,2-cryptand to a solution of [Na(NH3)6]+e− affords [Na (crown ether)]+e− or [Na(2,2,2-crypt)]+e−. Evaporation of these solutions yields a blue-black paramagnetic salt with the formula [Na(2,2,2-crypt)]+e−.

Most solid electride salts decompose above 240 K, although [Ca24Al28O64]4+(e−)4 is stable at room temperature.[3] In these salts, the electron is delocalized between the cations. Electrides are paramagnetic and Mott insulators. Properties of these salts have been analyzed.[4]

Reactions

Solutions of electride salts are powerful reducing agents, as demonstrated by their use in the Birch reduction. Evaporation of these blue solutions affords a mirror of Na. Such solutions slowly lose their colour as the electrons reduce ammonia:

2[Na(NH3)6]+e− → 2NaNH2 + 10NH3 + H2

This conversion is catalyzed by various metals.[5] An electride, [Na(NH3)6]+e−, is formed as a reaction intermediate.

High-pressure elements

Theoretical evidence supports electride behaviour in insulating high-pressure forms of potassium, sodium, and lithium. Here the isolated electron is stabilized by efficient packing, which reduces enthalpy under external pressure. The electride is identified by a maximum in the electron localization function, which distinguishes the electride from pressure-induced metallization. Electride phases are typically semiconducting or have very low conductivity,[6][7][8] usually with a complex optical response.[9] A sodium compound called disodium helide has been created under 113 gigapascals of pressure.[10]

gollark: The OpenSecurity ones are wireless, don't know about "SecurityCraft".
gollark: You'd even get no users!
gollark: You can even start your own node with cool different configs!
gollark: Okay, even if you don't need ATM-stolen levels of security, it still needs to be ridiculously secure.
gollark: Also, can you not, say, invisibly read from an RFID card someone had and take all their money?

See also

References
  1. Dye, J. L. (2003). "Electrons as Anions". Science. 301 (5633): 607–608. doi:10.1126/science.1088103. PMID 12893933.
  2. Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5
  3. Buchammagari, H.; et al. (2007). "Room Temperature-Stable Electride as a Synthetic Organic Reagent: Application to Pinacol Coupling Reaction in Aqueous Media". Org. Lett. 9 (21): 4287–4289. doi:10.1021/ol701885p. PMID 17854199.
  4. Wagner, M. J.; Huang, R. H.; Eglin, J. L.; Dye, J. L. Nature, 1994,368, 726-729.
  5. Greenlee, K. W.; Henne, A. L. (1946). Sodium Amide. Inorganic Syntheses. 2. pp. 128–135. doi:10.1002/9780470132333.ch38. ISBN 9780470132333.
  6. Marques M.; et al. (2009). "Potassium under Pressure: A Pseudobinary Ionic Compound". Physical Review Letters. 103 (11): 115501. Bibcode:2009PhRvL.103k5501M. doi:10.1103/PhysRevLett.103.115501. PMID 19792381.
  7. Gatti M.; et al. (2010). "Sodium: A Charge-Transfer Insulator at High Pressures". Physical Review Letters. 104 (11): 216404. arXiv:1003.0540. Bibcode:2010PhRvL.104u6404G. doi:10.1103/PhysRevLett.104.216404. PMID 20867123.
  8. Marques M.; et al. (2011). "Crystal Structures of Dense Lithium: A Metal-Semiconductor-Metal Transition" (PDF). Physical Review Letters. 106 (9): 095502. Bibcode:2011PhRvL.106i5502M. doi:10.1103/PhysRevLett.106.095502. PMID 21405633.
  9. Yu, Zheng; Geng, Hua Y.; Sun, Y.; Chen, Y. (2018). "Optical properties of dense lithium in electride phases by first-principles calculations". Scientific Reports. 8 (1): 3868. arXiv:1803.05234. Bibcode:2018NatSR...8.3868Y. doi:10.1038/s41598-018-22168-1. PMC 5832767. PMID 29497122.
  10. Wang, Hui-Tian; Boldyrev, Alexander I.; Popov, Ivan A.; Konôpková, Zuzana; Prakapenka, Vitali B.; Zhou, Xiang-Feng; Dronskowski, Richard; Deringer, Volker L.; Gatti, Carlo (May 2017). "A stable compound of helium and sodium at high pressure". Nature Chemistry. 9 (5): 440–445. arXiv:1309.3827. Bibcode:2017NatCh...9..440D. doi:10.1038/nchem.2716. ISSN 1755-4349. PMID 28430195.

Further reading
This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.