Sodium hydride is the chemical compound with the empirical formula sodiumhydrogen. This alkali metal hydride is primarily used as a strong yet combustible base in organic synthesis. NaH is a saline (salt-like) hydride, composed of Na+ and H− ions, in contrast to molecular hydrides such as borane, silane, germane, ammonia, and methane. It is an ionic material that is insoluble in all solvents (other than molten sodium metal), consistent with the fact that H− ions do not exist in solution.
Basic properties and structure
NaH is colorless, although samples generally appear grey. NaH is around 40% denser than Na (0.968 g/cm
3).
NaH, like lithium hydride, KH, rubidium hydride, and caesium hydride, adopts the sodium chloride crystal structure. In this motif, each Na+ ion is surrounded by six H− centers in an octahedral geometry. The ionic radius of H− (146 pm in NaH) and F− (133 pm) are comparable, as judged by the Na−H and Na−F distances.[Wells, A.F. (1984). Structural Inorganic Chemistry, Oxford: Clarendon Press]
"Inverse sodium hydride" (hydrogen sodide)
A very unusual situation occurs in a compound dubbed "inverse sodium hydride", which contains H
+ and Na
− ions. Na
− is an
alkalide, and this compound differs from ordinary sodium hydride in having a much higher energy content due to the net displacement of two electrons from hydrogen to sodium. A derivative of this "inverse sodium hydride" arises in the presence of the base [adamanzane|[3
6adamanzane]]. This molecule irreversibly encapsulates the H
+ and shields it from interaction with the alkalide Na
−.
Theoretical work has suggested that even an unprotected protonated tertiary amine complexed with the sodium alkalide might be metastable under certain solvent conditions, though the barrier to reaction would be small and finding a suitable solvent might be difficult.
Preparation
Industrially, NaH is prepared by introducing molten sodium into mineral oil with hydrogen at atmospheric pressure and mixed vigorously at ~8000 rpm. The reaction is especially rapid at 250−300 °C.
The resultant suspension of NaH in mineral oil is often directly used, such as in the production of
diborane.
Applications in organic synthesis
As a strong base
NaH is a base of wide scope and utility in organic chemistry.
[ Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. .] As a
superbase, it is capable of
deprotonating a range of even weak Brønsted acids to give the corresponding sodium derivatives. Typical "easy" substrates contain O-H, N-H, S-H bonds, including alcohols,
,
, and
.
NaH notably deprotonates carbon acids (i.e., C-H bonds) such as 1,3- such as . The resulting sodium derivatives can be alkylated. NaH is widely used to promote condensation reactions of carbonyl compounds via the Dieckmann condensation, Stobbe condensation, Darzens condensation, and Claisen condensation. Other carbon acids susceptible to deprotonation by NaH include sulfonium salts and DMSO. NaH is used to make sulfur , which in turn are used to convert into , as in the Johnson–Corey–Chaykovsky reaction.
As a reducing agent
NaH reduces certain main group compounds, but analogous reactivity is very rare in organic chemistry (
see below).
For early examples of NaH acting as a hydride donor, see ref. 3 therein. Notably boron trifluoride reacts to give
diborane and
sodium fluoride:
[Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. .]
- 6 NaH + 2 BF3 → B2H6 + 6 NaF
Si–Si and S–S bonds in and are also reduced.
A series of reduction reactions, including the hydrodecyanation of tertiary nitriles, reduction of imines to amines, and amides to aldehydes, can be effected by a composite reagent composed of sodium hydride and an alkali metal iodide (NaH⋅MI, M = Li, Na).
Hydrogen storage
Although not commercially significant sodium hydride has been proposed for hydrogen storage for use in
fuel cell vehicles. In one experimental implementation, plastic pellets containing NaH are crushed in the presence of water to release the hydrogen. One challenge with this technology is the regeneration of NaH from the NaOH formed by hydrolysis.
Practical considerations
Sodium hydride is sold as a mixture of 60% sodium hydride (w/w) in
mineral oil. Such a dispersion is safer to handle and weigh than pure NaH. The compound is often used in this form but the pure grey solid can be prepared by rinsing the commercial product with pentane or tetrahydrofuran, with care being taken because the waste solvent will contain traces of NaH and can ignite in air. Reactions involving NaH usually require air-free techniques.
Safety
NaH can
pyrophoricity. It also reacts vigorously with water or humid air to release
hydrogen, which is very flammable, and
sodium hydroxide (NaOH), a quite corrosive base. In practice, most sodium hydride is sold as a dispersion in
mineral oil, which can be safely handled in air.
Although sodium hydride is widely used in DMSO, DMF or DMAc for SN2 type reactions there have been many cases of fires and/or explosions from such mixtures.
[ UK Chemical Reaction Hazards Forum and references cited therein]
Cited sources
