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−
The cation [Na(NH3)6]+ is an octahedral coordination complex.
Solid salts
Addition of 2,2,2-cryptand to a solution of [Na(NH3)6]+e− affords [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.
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:
- [Na(NH3)6]+e− + NH3 → NaNH2 + H2
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.[4][5][6]
References
- ↑ Dye, J. L. (2003). "Electrons as Anions". Science 301 (5633): 607–608. doi:10.1126/science.1088103. PMID 12893933.
- ↑ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5
- ↑ Buchammagari, H.; et al. (2007). "Room Temperature-Stable Electride as a Synthetic Organic Reagent: Application to Pinacol Coupling Reaction in Aqueous Media". Org. Lett. (ACS Publications) 9 (21): 4287–4289. doi:10.1021/ol701885p. PMID 17854199.
- ↑ 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.
- ↑ 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.
- ↑ Marques M.; et al. (2011). "Crystal Structures of Dense Lithium: A Metal-Semiconductor-Metal Transition". Physical Review Letters 106 (9): 095502. Bibcode:2011PhRvL.106i5502M. doi:10.1103/PhysRevLett.106.095502.
Further reading
- J. L. Dye, M. J. Wagner, G. Overney, R. H. Huang, T. F. Nagy, and D. Tománek (1996). "Cavities and Channels in Electrides" (reprint). J. Am. Chem. Soc. 118 (31): 7329. doi:10.1021/ja960548z.